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| United States Patent |
6,001,783
|
|
Manka
, et al.
|
December 14, 1999
|
Mixed polysulfides and lubricants and functional fluids containing the
same
Abstract
This invention relates to a composition, comprising:
(A) at least one compound selected from the group consisting of
(A-1) a compound represented by the formula
T.sup.1 T.sup.2 --P(X.sup.1)--(S).sub.n --S--C (X.sup.2)--L.sup.1(A-I)
(A-2) a compound represented by the formula
T.sup.3 T.sup.4 --P(X.sup.3)--(S).sub.n --S--(DMTD)--S--J (A-II)
(A-3) a compound represented by the formula
L.sup.2 --C(X.sup.4)--(S).sub.n --S--(DMTD)--S--G (A-III)
and
(A-4) mixture of two or more of (A-1), (A-2) and (A-3);
wherein in Formulae (A-I), (A-II) and (A-III): (DMTD) is a
dimercaptothiadiazole nucleus; J is H, SR, --S--P(X.sup.5)--T.sup.5
T.sup.6 or --S--C(X.sup.6)-L.sup.3
G is H, SR or --S--C(X.sup.7)--L.sup.4
T.sup.1, T.sup.2, T.sup.3, T.sup.4, T.sup.5 and T.sup.6 are independently
R, SR or OR; L.sup.1, L.sup.2, L.sup.3 and L.sup.4 are independently R,
SR, OR or NRR; X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6 and
X.sup.7 are independently O or S; each R is independently a hydrocarbyl
group; and n is 1 to 4. In one embodiment, the inventive composition
further comprises (B) an acylated nitrogen-containing compound having a
substituent of at least about 10 aliphatic carbon atoms, (C) a phosphorus
compound, (D) a thiocarbamate, and/or (E) an organic sulfide other than
(A). The invention also relates to a lubricating composition or functional
fluid characterized by enhanced antiwear properties and comprising the
foregoing component (A) and, optionally, one or more of the foregoing
components (B), (C), (D) and/or (E).
| Inventors:
|
Manka; John S. (Euclid, OH);
Abraham; William D. (South Euclid, OH);
Roby; Stephen H. (Chesterland, OH);
Supp; James A. (Parma, OH);
Yodice; Richard (Mentor, OH)
|
| Assignee:
|
The Lubrizol Corporation (Wickliffe, OH)
|
| Appl. No.:
|
823467 |
| Filed:
|
March 24, 1997 |
| Current U.S. Class: |
508/428; 508/272; 508/273; 508/274; 508/430 |
| Intern'l Class: |
C10M 137/10; C10M 137/14 |
| Field of Search: |
548/112
508/272,273,274,276,428,430
|
References Cited
U.S. Patent Documents
| 2694682 | Nov., 1954 | Harle | 252/33.
|
| 2719827 | Oct., 1955 | Lowe | 252/47.
|
| 2743235 | Apr., 1956 | McDermott | 252/46.
|
| 2905639 | Sep., 1959 | Krzikalla et al. | 508/273.
|
| 3094548 | Jun., 1963 | Price et al. | 260/461.
|
| 3197405 | Jul., 1965 | LeSuer | 508/349.
|
| 3281507 | Oct., 1966 | Price et al. | 260/968.
|
| 3770854 | Nov., 1973 | Morris et al. | 260/985.
|
| 3844963 | Oct., 1974 | Elliott et al. | 508/428.
|
| 3904619 | Sep., 1975 | D'Amico | 260/246.
|
| 3914241 | Oct., 1975 | Elliott et al. | 508/273.
|
| 3980573 | Sep., 1976 | Okorodudu | 508/274.
|
| 4017168 | Apr., 1977 | Okorodudu | 260/302.
|
| 4039552 | Aug., 1977 | Brois et al. | 285/8.
|
| 4188299 | Feb., 1980 | Caspari | 508/274.
|
| 4234435 | Nov., 1980 | Meinhardt et al. | 252/51.
|
| 4417990 | Nov., 1983 | Clason et al. | 252/32.
|
| 4501679 | Feb., 1985 | Reierson et al. | 252/77.
|
| 4562259 | Dec., 1985 | Theobald et al. | 548/112.
|
| 4755311 | Jul., 1988 | Burjes et al. | 508/188.
|
| 4758362 | Jul., 1988 | Butke | 508/221.
|
| 5002674 | Mar., 1991 | Farng et al. | 252/32.
|
| 5256321 | Oct., 1993 | Todd | 252/32.
|
| Foreign Patent Documents |
| 937361 | Sep., 1963 | GB.
| |
Other References
Kato et al., "A Convenient Synthesis of Novel Unsymmetrical Acyl Thioacyl
Disulfides and Acyl O,O-Dialkylthiophosphoryl Disulfides," Synthesis,
1981, No. 5 pp. 370-371.
Kato et al., "Thioacylsulfenyl Bromides: Electrolytic dithiocarboxylating
Reagents," Tetrahedron Letters, 27 (38), 1986, pp. 4594-4598.
Boreca et al., "Synthesis and Chemical Properties of
Dialkoxyoxophosphoranesulfenates," Bull. Acad. Pol. Sci., Ser. Sci. Chem,
22 (3) 1974, pp. 201-205.
|
Primary Examiner: Johnson; Jerry D.
Attorney, Agent or Firm: Shold; David M.
Claims
We claim:
1. A lubricant or functional fluid comprising a major amount of an oil of
lubricating viscosity and a minor amount of at least one compound
represented by the formula
T.sup.1 T.sup.2 --P(X.sup.1)--(S).sub.n --S--C(X.sup.2)--L.sup.1(A-I)
wherein in Formula (A-I):
T.sup.1 and T.sup.2 are independently R, SR or OR;
L.sup.1 is R, SR, OR or NRR;
X.sup.1 and X.sup.2 are independently O or S;
each R is independently a hydrocarbyl group; and
n is 1 to 4.
2. The lubricant or functional fluid of claim 1 wherein in Formula (A-I),
T.sup.1 and T.sup.2 are each OR, X.sup.1 is S, and n is 1 or 2.
3. The lubricant or functional fluid of claim 1 wherein in Formula (A-I),
T.sup.1 and T.sup.2 are each SR, X.sup.1 is S, and n is 1 or 2.
4. The lubricant or functional fluid of claim 1 wherein in Formula (A-I),
X.sup.2 is S, L.sup.1 is SR, and n is 1 or 2.
5. The lubricant or functional fluid of claim 1 wherein in Formula (A-I),
X.sup.2 is S, L.sup.1 is OR, and n is 1 or 2.
6. The lubricant or functional fluid of claim 1 wherein in Formula (A-I),
X.sup.2 is S, L.sup.1 is NRR, and n is 1 or 2.
7. The lubricant or functional fluid of claim 1 wherein in Formula (A-I), n
is 1.
8. The lubricant or functional fluid of claim 1 further comprising one or
more of:
a compound represented by the formula
T.sup.3 T.sup.4 --P(X.sup.3)--(S).sub.n --S--(DMTD)--S--J (A-II)
and
a compound represented by the formula
L.sup.2 --C--(X.sup.4)--(S).sub.n --S--(DMTD)--S--G (A-III)
wherein:
DMTD is a thiadiazole nucleus;
J is H, SR, --S--P(X.sup.5)--T.sup.5 T.sup.6 or --S--C(X.sup.6)--L.sup.3 ;
G is H, SR or --S--C(X.sup.7)--L.sup.4 ;
T.sup.3, T.sup.4, T.sup.5, and T.sup.6 are independently R, SR, or OR;
L.sup.2, L.sup.3 and L.sup.4 are independently R, SR, OR, or NRR;
X.sup.3, X.sup.4, X.sup.5, X.sup.6, and X.sup.7 are independently O or S;
each R is independently a hydrocarbyl group; and
n is 1 to 4.
9. The lubricant or functional fluid of claim 1 further comprising:
(B) an acylated nitrogen-containing compound having a substituent of at
least about 10 aliphatic carbon atoms.
10. The lubricant or functional fluid of claim 9 wherein (B) is derived
from a substituted succinic acid or anhydride and at least one alkylene
polyamine, the substituent groups on said succinic acid or anhydride being
derived from polybutene in which at least about 50% of the total units
derived from butenes are derived from isobutylene, said polybutene being
characterized by an Mn value of about 1500 to about 2000 and an Mw/Mn
value of about 3 to about 4, said acid or anhydride being characterized
within its structure of an average of about 1.5 to about 2.5 succinic
groups for each equivalent weight of substituent groups.
11. The lubricant or functional fluid of claim 9 wherein (B) is derived
from a substituted succinic acid or anhydride and at least one alkylene
polyamine, the substituent groups on said succinic acid or anhydride being
derived from polybutene in which at least about 50% of the total units
derived from butenes are derived from isobutylene, said polybutene being
characterized by an Mn value of about 800 to about 1200 and an Mw/Mn value
of about 2 to about 3, said acid or anhydride being characterized within
its structure of an average of about 0.9 to about 1.2 succinic groups for
each equivalent weight of substituent groups.
12. The lubricant or functional fluid of claim 1 further comprising:
(C) a phosphorus compound other than (A-I).
13. The lubricant or functional fluid of claim 12 wherein (C) is a compound
represented by the formula
##STR16##
wherein in Formula (C-IV), R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently hydrocarbyl groups, X.sup.1 and X.sup.2 are independently O
or S, and n is zero to 3.
14. The lubricant or functional fluid of claim 12 wherein (C) is a
phosphorus acid, phosphorus acid ester, phosphorus acid salt, or
derivative thereof.
15. The lubricant or functional fluid of claim 12 wherein (C) is a compound
represented by the formula
##STR17##
wherein in Formula (C-I), R.sup.1, R.sup.2 and R.sup.3 are independently
hydrogen or hydrocarbyl groups, X is O or S, and a, b and c are
independently zero or 1.
16. The lubricant or functional fluid of claim 12 wherein (C) is a compound
represented by the formula
##STR18##
wherein in Formula (C-II), R.sup.1, R.sup.2 and R.sup.3 are independently
hydrogen or hydrocarbyl groups, and a, b and c are independently zero or
1.
17. The lubricant or functional fluid of claim 12 wherein (C) is a compound
represented by the formula
##STR19##
wherein in Formula (C-III): X.sup.1, X.sup.2 and X.sup.3 and X.sup.4 are
independently O or S, and X.sup.1 and X.sup.2 can be NR.sup.4 ; a and b
are independently zero or 1; and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently hydrocarbyl groups, and R.sup.3 and R.sup.4 can be hydrogen;
or a metal, amine or ammonium salt of said compound represented by Formula
(C-III).
18. The lubricant or functional fluid of claim 17 wherein said compound
represented by Formula (C-III) is a metal salt, said metal being a Group
IA, IIA or IIB metal, aluminum, tin, iron, cobalt, lead, molybdenum,
manganese, nickel, antimony, bismuth, or a mixture of two or more thereof.
19. The lubricant or functional fluid of claim 17 wherein said compound
represented by Formula (C-III) is a metal salt, said metal being zinc.
20. The lubricant or functional fluid of claim 1 further comprising:
(D) a compound represented by the formula
R.sup.1 R.sup.2 N--C(X)S--(CR.sup.3 R.sup.4).sub.a Z (D-I)
wherein in Formula (D-I), R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently hydrogen or hydrocarbyl groups, provided that at least one
of R.sup.1 and R.sup.2 is a hydrocarbyl group; X is O or S; a is 1 or 2,
provided that when a is 2, each CR.sup.3 R.sup.4 can be the same or
different; and Z is a hydrocarbyl group, a hetero group, a hydroxy
hydrocarbyl group, an activating group, or a --(S)C(X)NR.sup.1 R.sup.2
group; provide that when a is 2, Z is an activating group.
21. The lubricant or functional fluid of claim 20 wherein (D) is a compound
represented by the formula
##STR20##
wherein in Formula (D-II), R.sup.1, R.sup.2 and R.sup.5 are independently
hydrocarbyl groups.
22. The lubricant or functional fluid of claim 20 wherein (D) is a compound
represented by the formula
##STR21##
23. The lubricant or functional fluid of claim 1 further comprising: (E) a
compound represented by the formula
##STR22##
wherein in Formula (E-I), T.sup.1 and T.sup.2 are independently R, OR, SR
or NRR wherein each R is independently a hydrocarbyl group, X.sup.1 and
X.sup.2 are, independently O or S, and n is zero to 3.
24. The lubricant or functional fluid of claim 1 further comprising a
corrosion-inhibiting agent, detergent, dispersant, antioxidant, viscosity
improving agent, antiwear agent, extreme-pressure agent, pour-point
depressant, friction-modifier, fluidity-modifier, anti-foam agent, or
mixture of two or more thereof.
25. The lubricant of functional fluid of claim 1 in the form of an engine
lubricating oil.
26. A method for lubricating an internal combustion engine comprising
supplying to such engine the engine lubricating oil of claim 25.
27. The lubricant or functional fluid of claim 1 in the form of a gear oil.
28. The lubricant of functional fluid of claim 1 in the form of a grease.
29. A process for making a lubricant or a functional fluid comprising
mixing an oil of lubricating viscosity with at least one compound
represented by the formula
T.sup.1 T.sup.2 --P(X.sup.1)--(S).sub.n --S--C(X.sup.2)--L.sup.1(A-I)
wherein in Formula (A-I):
T.sup.1 and T.sup.2 are independently R, SR or OR;
L.sup.1 is R, SR, OR or NRR;
X.sup.1 and X.sup.2 are independently O or S;
each R is independently a hydrocarbyl group; and
n is 1 to 4.
Description
TECHNICAL FIELD
This invention relates to certain mixed polysulfides, and to lubricants and
functional fluids containing such mixed polysulfides. The lubricants and
functional fluids are characterized by enhanced antiwear properties.
BACKGROUND OF THE INVENTION
Engine lubricating oils require the presence of additives to protect the
engine from wear. For almost 40 years, the principal antiwear additive for
engine lubricating oils has been zinc dialkyl dithiophosphate (ZDDP).
However, ZDDP is typically used in the lubricating oil at a sufficient
concentration to provide a phosphorus content of 0.12% by weight or higher
in order to pass required industry standard tests for antiwear. Since
phosphates may result in the deactivation of emission control catalysts
used in automotive exhaust systems, a reduction in the amount of
phosphorus-containing additives (e.g., ZDDP) in the oil would be
desirable. The problem sought to be overcome is to provide for a reduction
in the amount of phosphorus-containing additive in the lubricating oil and
yet provide the lubricating oil with desired antiwear properties. The
present invention provides a solution to this problem by providing
compositions that can function as either a partial or complete replacement
for ZDDP.
The use of ashless dispersants in lubricants is disclosed in numerous
patents, including U.S. Pat. Nos. 3,172,892; 3,219,666; 3,272,746;
3,310,492; 3,341,542; 3,444,170; 3,455,831; 3,455,832; 3,576,743;
3,630,904; 3,632,511; 3,804,763; and 4,234,435.
The use of metal salts of phosphorodithioic acids as additives for
lubricants is disclosed in U.S. Pat. Nos. 4,263,150; 4,289,635; 4,308,154;
4,322,479; and 4,417,990. Amine salts of such acids are disclosed as being
useful as additives for grease compositions in U.S. Pat. No. 5,256,321.
U.S. Pat. No. 4,758,362 discloses the addition of a carbamate to a low
phosphorus or phosphorus free lubricating oil composition to provide a
composition with enhanced extreme-pressure and antiwear properties.
The use of disulfides represented by the formula (R.sub.z YC.dbd.S).sub.2
S.sub.2, wherein Y is O, S or N, and z is 1 when Y is O or S and 2 when Y
is N, as lubricant additives is disclosed in U.S. Pat. Nos. 2,681,316;
2,691,632; and 2,694,682.
U.S. Pat. No. 2,307,307 discloses the use of compounds represented by the
formula (RXC.dbd.S).sub.2 S.sub.n, wherein X is O or S, and n is greater
than 2, as lubricant additives.
The use of compounds represented by the formula (ROC.dbd.S)S.sub.2 in
lubricants for use on bearing surfaces is disclosed in U.S. Pat. Nos.
2,110,281 and 2,206,245. U.S. Pat. No. 2,431,010 discloses the use of
compounds represented by the formula (ROC.dbd.S)S.sub.n, wherein n is 2-4,
as soluble cutting oil additives.
The use of thiuram sulfides as lubricant additives is disclosed in U.S.
Pat. Nos. 2,081,886; 2,201,258; 3,249,542; 3,352,781; 4,207,196; and
4,501,678.
U.S. Pat. No. 5,034,141 discloses that improved antiwear results can be
obtained by combining a thiodixanthogen (e.g., octylthiodixanthogen) with
a metal thiophosphate (e.g., ZDDP). U.S. Pat. No. 5,034,142 discloses the
addition of a metal alkoxyalkylxanthate (e.g., nickel
ethoxyethylxanthate), a dixanthogen (e.g., diethoxyethyl dixanthogen) and
a metal thiophosphate (e.g., ZDDP) to a lubricant to improve antiwear.
European patent application 0 609 623 A1 discloses an engine oil
composition containing a metal-containing detergent, zinc dithiophosphate,
a boron-containing ashless dispersant, aliphatic amide compound, and
either a dithiocarbamate compound or an ester derived from a fatty acid
and boric acid. Among the dithiocarbamates that are disclosed are sulfides
and disulfides.
SUMMARY OF THE INVENTION
This invention relates to a composition, comprising:
(A) at least one compound selected from the group consisting of
(A-1) a compound represented by the formula
T.sup.1 T.sup.2- P(X.sup.1)--(S).sub.n --S--C(X.sup.2)--L.sup.1(A-I)
(A-2) a compound represented by the formula
T.sup.3 T.sup.4 --P(X.sup.3)--(S).sub.n --S--(DMTD)--S--J (A-II)
(A-3) a compound represented by the formula
L.sup.2 --C(X.sup.4)--(S).sub.n --S--(DMTD)--S--G (A-III)
and
(A-4) mixture of two or more of (A-1), (A-2) and (A-3);
wherein in Formulae (A-I), (A-II) and (A-III):
(DMTD) is a dimercaptothiadiazole nucleus;
J is H, SR, --S--P (X.sup.5)--T.sup.5 T.sup.6 or --S--C (X.sup.6)--L.sup.3
;
G is H, SR or --S--C (X.sup.7)--L.sup.4 ;
T.sup.1, T.sup.2, T.sup.3, T.sup.4, T.sup.5 and T.sup.6 are independently
R, SR or OR;
L.sup.1, L.sup.2, L.sup.3 and L.sup.4 are independently R, SR, OR or NRR;
X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6 and X.sup.7 are
independently O or S;
each R is independently a hydrocarbyl group; and
n is 1 to 4.
In one embodiment, the inventive composition further comprises (B) an
acylated nitrogen-containing compound having a substituent of at least
about 10 aliphatic carbon atoms. In one embodiment, the inventive
composition further comprises (C) a phosphorus compound. In one
embodiment, the inventive composition further comprises (D) a
thiocarbamate. In one embodiment, the inventive composition further
comprises (E) an organic sulfide. In one embodiment, the inventive
compositions are lubricating compositions or functional fluids
characterized by enhanced antiwear properties and comprising the foregoing
component (A) and, optionally, one or more of the foregoing components
(B), (C), (D) and/or (E). In one embodiment, the invention relates to a
process comprising mixing the foregoing component (A) with an oil of
lubricating viscosity and, optionally, one or more of the foregoing
components (B), (C), (D) and/or (E).
In one embodiment, the inventive lubricating compositions and functional
fluids are characterized by reduced phosphorus levels when compared to
those in the prior art, and yet have sufficient antiwear properties to
pass industry standard tests for antiwear. The inventive lubricating
compositions and functional fluids are especially suitable for use as
engine lubricating oil compositions, gear oil compositions and grease
compositions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As used in this specification and in the appended claims, the terms
"hydrocarbyl" and "hydrocarbon based" denote a group having a carbon atom
directly attached to the remainder of the molecule and having a
hydrocarbon or predominantly hydrocarbon character within the context of
this invention. Such groups include the following:
(1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and al
cyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic
groups, and the like, as well as cyclic groups wherein the ring is
completed through another portion of the molecule (that is, any two
indicated substituents may together form an alicyclic group). Such groups
are known to those skilled in the art. Examples include methyl, ethyl,
octyl, decyl, octadecyl, cyclohexyl, phenyl, etc.
(2) Substituted hydrocarbon groups; that is, groups containing
non-hydrocarbon substituents which, in the context of this invention, do
not alter the predominantly hydrocarbon character of the group. Those
skilled in the art will be aware of suitable substituents. Examples
include halo, hydroxy, nitro, cyano, alkoxy, acyl, etc.
(3) Hetero groups; that is, groups which, while predominantly hydrocarbon
in character within the context of this invention, contain atoms other
than carbon in a chain or ring otherwise composed of carbon atoms.
Suitable hetero atoms will be apparent to those skilled in the art and
include, for example, nitrogen, oxygen and sulfur.
In general, no more than about three substituents or hetero atoms, and
preferably no more than one, will be present for each 10 carbon atoms in
the hydrocarbyl group.
Terms such as "alkyl-based," "aryl-based," and the like have meanings
analogous to the above with respect to alkyl groups, aryl groups and the
like.
The term "hydrocarbon-based" has the same meaning and can be used
interchangeably with the term hydrocarbyl when referring to molecular
groups having a carbon atom attached directly to the remainder of a
molecule.
The term "lower" as used herein in conjunction with terms such as
hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is intended to describe
such groups which contain a total of up to 7 carbon atoms.
The term "oil-soluble" refers to a material that is soluble in mineral oil
to the extent of at least about one gram per liter at 25.degree. C.
(A) Mixed Polysulfides
The compounds (A) are mixed polysulfides. These compounds are selected from
the group consisting of
(A-1) a compound represented by the formula
T.sup.1 T.sup.2 --P(X.sup.1)--(S).sub.n --S--C(X.sup.2)--L.sup.1(A-I)
(A-2) a compound represented by the formula
T.sup.3 T.sup.4 --P(X.sup.3)--(S).sub.n --S--DMTD)--S--J (A-II)
(A-3) a compound represented by the formula
L.sup.2 --C(X.sup.4)--(S).sub.n --S--(DMTD)--S--G (A-III)
and
(A-4) mixture of two or more of (A-1), (A-2) and (A-3).
In Formulae (A-I), (A-II) and (A-III), the notation "(DMTD)" refers to a
thiadiazole nucleus of dimercaptothiadiazole. J is H, SR, --S--P
(X.sup.5)--T.sup.5 T.sup.6 or --S--C (X.sup.7)--L.sup.3 ;
G is H, SR or --S--C (X.sup.7)--L.sup.4
T.sup.1, T.sup.2, T.sup.3, T.sup.4, T.sup.5 and T.sup.6 are independently
R, SR or OR. L.sup.1, L.sup.2, L.sup.3 and L.sup.4 are independently R,
SR, OR or NRR. X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6 and
X.sup.7 are independently O or S. Each R is independently a hydrocarbyl
group. n is 1 to 4, and in one embodiment 1 or 2, and in one embodiment n
is 1.
The di-mercaptothiadiazole nucleus, (DMTD), utilized in Formulae (A-II) or
(A-III) has one or more of the structures:
##STR1##
In a preferred embodiment, (DMTD) has the structure:
##STR2##
The R groups in Formulae (A-I), (A-II) and (A-III) are hydrocarbyl groups
of sufficient length to provide the compounds with a measure of oil
solubility. When two or more R groups are present in a single compound,
the total number of carbon atoms should be sufficient to provide the
compound with such solubility. Generally, each R group will have 1 to
about 50 carbon atoms, and in one embodiment 1 to about 30 carbon atoms,
and in one embodiment 1 to about 18 carbon atoms, and in one embodiment 1
to about 12 carbon atoms, and in one embodiment 1 to about 8 carbon atoms.
Examples of R groups that can be used include methyl, ethyl, propyl,
isopropyl, butyl, n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, ethyl hexyl,
octyl, isooctyl, decyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl,
phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl,
alkylphenylalkyl, alkylnaphthylalkyl, and mixtures thereof.
In one embodiment, component (A) is a compound represented by Formula
(A-I), and T.sup.1 and T.sup.2 are each OR, X.sup.1 is S, and n is 1 or 2.
In one embodiment, T.sup.1 and T.sup.2 are each SR, X.sup.1 is S, and n is
1 or 2. In one embodiment, X.sup.2 is S, L.sup.1 is SR, and n is 1 or 2.
In one embodiment, X.sup.2 is S, L.sup.1 is OR, and n is 1 or 2. In one
embodiment, X.sup.2 is S, L.sup.1 is NRR, and n is 1 or 2.
Specific compounds of the type represented by Formula (A-I) are disclosed
in the following Table I.
TABLE I
______________________________________
T.sup.1 T.sup.2 -P (X.sup.1)--(S).sub.n --S--C(X.sup.2)-L.sup.1 (A-I)
T.sup.1
T.sup.2 X.sup.1
n X.sup.2
L.sup.1
______________________________________
RO RO S 1 S OR
RO RO S 1 S SR
RO RO S 1 S NRR
RO RO S 1 S R
RS RS S 1 O OR
RS RS S 1 O SR
RS RS S 1 O NRR
RS RS S 1 O R
RO RO O 1 S OR
RO RO O 1 S SR
RO RO O 1 S NRR
RO RO O 1 O OR
RO RO O 1 O SR
RO RO O 1 O NRR
RS RO S 1 S OR
RS RO S 1 S SR
RS RO S 1 S NRR
______________________________________
Each R is independently isopropyl, butyl, nbutyl, isobutyl, amyl,
4methyl-2-pentyl, ethylhexyl, octyl, isooctyl, decyl, dodecyl, tetradecyl
2pentenyl, dodecenyl, phenyl or naphthyl.
In one embodiment, component (A) is a compound represented by the formula:
T.sup.1 T.sup.2 --P(S)--S--S--C(S)--L.sup.1 (A-IA)
wherein in Formula (A-IA), T.sup.1 and T.sup.2 are the same or different
and each is SR or OR, L.sup.1 is SR, OR, or NRR, and each R is
independently a hydrocarbyl group.
In one embodiment, component (A) is a compound represented by Formula
(A-II), and T.sup.3 and T.sup.4 are each OR, X.sup.3 is S, and n is 1 or
2. In one embodiment, n is 1 or 2 and J is H or --S--C (X.sup.6)--L.sup.3.
In one embodiment, n is 1 or 2 and J is --S--P (X.sup.5)--T.sup.5 T.sup.6.
In one embodiment, n is 1, T.sup.3 and T.sup.4 are independently OR,
X.sup.3 is S, and J is SR. In one embodiment, n is 1, T.sup.3 and T.sup.4
are independently OR, X.sup.3 is S, and J is H or --S--C
(X.sup.6)--L.sup.3
In one embodiment, n is 1, T.sup.3 and T.sup.4 are independently OR,
X.sup.3 is S, and J is H or --S--P (X.sup.5)--T.sup.5 T.sup.6
Specific compounds of the type represented by Formula (A-II) are disclosed
in the following Table II.
TABLE II
______________________________________
T.sup.3 T.sup.4 -P (X.sup.3)--(S).sub.n --S-(DMTD)-S-J (A-II)
T.sup.3
T.sup.4 X.sup.3
n J
______________________________________
RO RO S 1 H
RO RO S 1 SR
RO RO S 1 S--C(.dbd.S)OR
RO RO S 1 S--P(.dbd.S)(OR).sub.2
RO RO O 1 H
RO RO O 1 SR
RO RO O 1 S--C(.dbd.S)OR
RO RO O 1 S--P(.dbd.S)(OR).sub.2
RS RO S 1 H
RS RO O 1 H
RS RO S 1 S--C(.dbd.S)OR
RS RO S 1 S--P(.dbd.S)(R).sub.2
RS RO O 1 S--C(.dbd.S)OR
RS RO O 1 S--P(.dbd.S)(OR).sub.2
RO RO S 1 S--C(.dbd.S)SR
RO RO S 1 S--P(.dbd.S)(SR).sub.2
______________________________________
Each R is independently isopropyl, butyl, nbutyl, isobutyl, amyl,
4methyl-2-pentyl, ethylhexyl, octyl, isooctyl, decyl, dodecyl, tetradecyl
2pentenyl, dodecenyl, phenyl or naphthyl.
With each of the foregoing compounds, (DMTD) has the following structural
formula:
##STR3##
In one embodiment, component (A) is a compound represented by the formula
##STR4##
wherein in Formula (A-IIA), J is H or --S--P (S)--(O--R).sub.2 and each R
is independently a hydrocarbyl group. In one embodiment, J is H, --S--C
(S)--S--R, --S--C (S)--O--R, or --S--C (S)--NRR and each R is
independently a hydrocarbyl group.
In one embodiment, component (A) is a compound represented by Formula
(A-III), and n is 1 or 2, T.sup.6 is SR, X.sup.4 is S, and G is H or
--S--C (X.sup.7)--T.sup.10.
In one embodiment, n is 1 or 2, L.sup.2 is OR, X.sup.4 is S, and G is H or
--S--C (X.sup.7)--L.sup.4.
In one embodiment, n is 1, L.sup.2 is SR or OR, X.sup.4 is S, and G is H or
--S--C (X.sup.7)--L.sup.4.
In one embodiment, n is 1, L.sup.2 is SR or OR, X.sup.4 is S, and G is SR.
Specific compounds of the type represented by Formula (A-III) are disclosed
in the following Table III.
TABLE III
______________________________________
L.sup.2 --C(X.sup.4)-(S).sub.n --S--(DMTD)--S--G (A-III)
L.sup.2 X.sup.4
n G
______________________________________
RO S 1 H
RO S 1 SR
RO S 1 SC(.dbd.S)R
RO S 1 SC(.dbd.S)SR
RO 5 1 SC(.dbd.S)OR
RO 5 1 SC(.dbd.S)NRR
RS 5 1 H
RS 5 1 SR
RS 5 1 SC(.dbd.S)R
RS S 1 SC(.dbd.S)SR
RS S 1 SC(.dbd.S)OR
RS S 1 SC(.dbd.S)NRR
RO O 1 H
RO O 1 SR
RO O 1 SC(.dbd.S)R
RO O 1 SC(.dbd.S)SR
RO O 1 SC(.dbd.S)OR
RO O 1 SC(.dbd.S)NRR
______________________________________
Each R is independently isopropyl, butyl, nbutyl, isobutyl, amyl,
4methyl-2-pentyl, ethylhexyl, octyl, isooctyl, decyl, dodecyl, tetradecyl
2pentenyl, dodecenyl, phenyl or naphthyl. With each of the foregoing
compounds, (DMTD) has the following structural formula:
##STR5##
In one embodiment, component (A) is a compound represented by the formula
##STR6##
wherein Formula (AIIIA), L.sup.2 is SR, OR or NRR, and G is H, SR, --S--C
(S)--S--R, --S--C (S)--O--R, or --S--C (S)--NRR and each R is
independently a hydrocarbyl group.
The compounds represented by Formula (AI) can be prepared by combining an
appropriate halogenated hydrocarbon, mercaptan, alcohol or amine with an
alkali metal reagent (e.g., NaOH, KOH), and a phosphoruscontaining acid
represented by the formula
T.sup.1 T.sup.2 --P(X.sup.1)--SH (P-1)
wherein in Formula (P-1), T.sup.1, T.sup.2 and X.sup.1 are the same as in
Formula (A-I). The resulting mixture is reacted with carbon disulfide and
then an oxidizing agent (e.g., hydrogen peroxide, cobalt
maleonitriledithioate, K.sub.2 Fe(CN).sub.6, FeCl.sub.3,
dimethylsulfoxide, dithiobis(thioformate), copper sulfate, etc.), sulfur
dichloride or sulfur monochloride to form the desired polysulfide
compound. The oxygen-containing analogs of these compounds wherein X.sup.1
and X.sup.2 in Formula (A-I) are oxygen can be prepared by treating the
sulfur-containing compounds with water or steam.
When J is --S--P (X.sup.5)--T.sup.5 T.sup.6 in Formula (A-II), the
compounds represented by such Formula (A-II) can be prepared by reacting a
phosphorus-containing acid represented by the formula
T.sup.3 T.sup.4 --P(X.sup.3)--SH (P-2)
wherein in Formula (P-2), T.sup.3, T.sup.4 and X.sup.3 are the same as in
Formula (A-II), a phosphorus-containing acid represented by the formula
T.sup.5 T.sup.6 --P(X.sup.5)--SH (P-3)
wherein in Formula (P-3), T.sup.5, T.sup.6 and X.sup.5 are the same as in
Formula (A-II), and a dimercaptothiadiazole with an oxidizing agent (e.g.,
hydrogen peroxide, cobalt maleonitriledithioate, K.sub.2 Fe(CN).sub.6,
FeCl.sub.3, dimethylsulfoxide, dithiobis(thioformate), copper sulfate,
etc), sulfur dichloride or sulfur monochloride to form the desired
polysulfide compound. The phosphorus-containing acids represented by the
Formulae (P-2) and (P-3) can be the same or different and preferably are
the same. The oxygen-containing analogs of these compounds wherein X.sup.3
and X.sup.5 in Formula (A-II)are oxygen can be prepared by treating the
sulfur-containing compounds with water or steam.
When J is --S--C (X.sup.6)--L.sup.3 in Formula (A-II), the compounds
represented by such Formula (A-II) can be prepared by combining a
dimercaptothiadiazole, an appropriate halogenated hydrocarbon, mercaptan,
alcohol or amine, an alkali metal reagent (e.g., NaOH, KOH), and a
phosphorus-containing acid represented by the formula
T.sup.3 T.sup.4 --P(X.sup.3)--SH (P-2)
wherein in Formula (P-2), T.sup.3, T.sup.4 and X.sup.3 are the same as in
Formula (A-II). The resulting mixture is reacted with carbon disulfide and
then an oxidizing agent (e.g., hydrogen peroxide, cobalt
maleonitriledithioate, K.sub.2 Fe(CN).sub.6, FeCl.sub.3,
dimethylsulfoxide, dithiobis(thioformate), copper sulfate, etc.), sulfur
dichloride or sulfur monochloride to form the desired polysulfide
compound. The oxygen-containing analogs of these compounds wherein X.sup.3
and X.sup.6 in Formula (A-II) are oxygen can be prepared by treating the
sulfur-containing compounds with water or steam.
When J is SR in Formula (A-II), the compounds represented by such Formula
(A-II)can be prepared by combining a dimercaptothiadiazole, an appropriate
mercaptan, an alkali metal reagent (e.g., NaOH, KOH), and a
phosphorus-containing acid represented by the formula
T.sup.3 T.sup.4 --P(X.sup.3)--SH (P-2)
wherein in Formula (P-2), T.sup.3, T.sup.4 and X.sup.3 are the same as in
Formula (A-II). The resulting mixture is reacted with an oxidizing agent
(e.g., hydrogen peroxide, cobalt maleonitriledithioate, K.sub.2
Fe(CN).sub.6, FeCl.sub.3, dimethylsulfoxide, dithiobis(thioformate),
copper sulfate, etc.), sulfur dichloride or sulfur monochloride to form
the desired polysulfide compound. The oxygen-containing analogs of these
compounds wherein X.sup.3 in Formula (A-II)is oxygen can be prepared by
treating the sulfur-containing compounds with water or steam.
When J is H in Formula (A-II), the compounds represented by such Formula
(A-II)can be prepared by combining a dimercaptothiadiazole, an alkali
metal reagent (e.g., NaOH, KOH), and a phosphorus-containing acid
represented by the formula
T.sup.3 T.sup.4 --P (X.sup.3)--SH (P-2)
wherein in Formula (P-2), T.sup.3, T.sup.4 and X.sup.3 are the same as in
Formula (A-II). The resulting mixture is reacted with an oxidizing agent
(e.g., hydrogen peroxide, cobalt maleonitriledithioate, K.sub.2
Fe(CN).sub.6,FeCl.sub.3, dimethylsulfoxide, dithiobis(thioformate), copper
sulfate, etc.), sulfur dichloride or sulfur monochloride to form the
desired polysulfide compound. The oxygen-containing analogs of these
compounds wherein X.sup.3 in Formula (A-II)is oxygen can be prepared by
treating the sulfur-containing compounds with water or steam.
The compounds represented by Formula (A-III) can be prepared by combining
an appropriate halogenated hydrocarbon, mercaptan, alcohol or amine with
an alkali metal reagent (e.g., NaOH, KOH), and a dimercaptothiadiazole and
reacting the resulting mixture with an oxidizing agent (e.g., hydrogen
peroxide, cobalt maleonitriledithioate, K.sub.2 Fe(CN).sub.6, FeCl.sub.3,
dimethylsulfoxide, dithiobis(thioformate), copper sulfate, etc), sulfur
dichloride or sulfur monochloride to form the desired polysulfide
compound. The oxygen-containing analogs of these compounds wherein X.sup.4
and X.sup.7 in Formula (A-III) are oxygen can be prepared by treating the
sulfur-containing compounds with water or steam.
The phosphorus-containing acids represented by the Formulae (P-1), (P-2)
and (P-3) are known in the art. The acids wherein X.sup.1, X.sup.3 and
X.sup.5, respectively, are sulfur and T.sup.1 and and T.sup.2, and T.sup.3
and T.sup.4, and T.sup.5 and T.sup.6, respectively, are OR, can be
obtained by the reaction of phosphorus pentasulfide (P.sub.2 S.sub.5) and
an alcohol or mixture of alcohols corresponding to T.sup.1 and T.sup.2,
T.sup.3 and T.sup.4, or T.sup.5 and T.sup.6, respectively. The reaction
involves mixing at a temperature of about 20.degree. C. to about
200.degree. C., four moles of alcohol with one mole of phosphorus
pentasulfide. Hydrogen sulfide is liberated in this reaction. The
oxygen-containing analogs of these compounds can be prepared by treating
the dithioic acid with water or steam.
The halogenated hydrocarbons that can be used to prepare the compounds
represented by Formulae (A-I), (A-II)or (A-III) include chlorinated or
brominated hydrocarbons of 1 to about 50 carbon atoms, and in one
embodiment 1 to about 30 carbon atoms, and in one embodiment 1 to about 18
carbon atoms, and in one embodiment 1 to about 12 carbon atoms, and in one
embodiment 1 to about 8 carbon atoms. Specific examples include the
methyl, ethyl, propyl, isopropyl, butyl, n-butyl, isobutyl, amyl,
4-methyl-2-pentyl, octyl, isooctyl, decyl, dodecyl, tetradecyl,
2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl,
phenylalkyl, naphthylalkyl, alkylphenylalkyl and alkylnaphtylalkyl
chlorides and bromides.
The mercaptans that can be used include the hydrocarbyl mercaptans
represented by the formula R--S--H, wherein R is as defined above in
Formulae (A-I), (A-II)or (A-III). In one embodiment, R is an alkyl, an
alkenyl, cycloalkyl, or cycloalkenyl group. R may be an aryl (e.g.,
phenyl, naphthyl), alkylaryl, arylalkyl or alkylaryl alkyl group. R may
also be a haloalkyl, hydroxyalkyl, or hydroxyalkyl-substituted (e.g.,
hydroxymethyl, hydroxyethyl, etc.) aliphatic group. In one embodiment, R
contains from about 2 to about 30 carbon atoms, or from about 2 to about
24, or from about 3 to about 18 carbon atoms. Examples include butyl
mercaptan, amyl mercaptan, hexyl mercaptan, octyl mercaptan,
6-hydroxymethyloctanethiol, nonyl mercaptan, decyl mercaptan,
10-amino-dodecanethiol, dodecyl mercaptan,
10-hydroxymethyl-tetradecanethiol, and tetradecyl mercaptan.
Alcohols used to prepare the compounds of Formulae (A-I), (A-II) or (A-III)
include isopropyl, n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, hexyl,
isooctyl, decyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl, aromatic
alcohols such as the phenols, etc. Higher synthetic monohydric alcohols of
the type formed by Oxo process (e.g., 2-ethylhexyl), the Aldol
condensation, or by organo- aluminum catalyzed oligomerization of
alpha-olefins (especially ethylene), followed by oxidation and hydrolysis,
also are useful. Examples of useful monohydric alcohols and alcohol
mixtures include the commercially available "Alfol" alcohols marketed by
Continental Oil Corporation. Alfol 810 is a mixture of alcohols containing
primarily straight chain, primary alcohols having from 8 to 10 carbon
atoms. Alfol 12 is a mixture of alcohols containing mostly C.sub.12 fatty
alcohols. Alfol 1218 is a mixture of synthetic, primary, straight-chain
alcohols containing primarily 12 to 18 carbon atoms. The Alfol 20+
alcohols are mixtures of C.sub.18 -C.sub.28 primary alcohols having
mostly, on an alcohol basis, C.sub.20 alcohols as determined by GLC
(gas-liquid-chromatography). The Alfol 22+ alcohols are C.sub.18 -C.sub.28
primary alcohols containing primarily, on an alcohol basis, C.sub.22
alcohols. These Alfol alcohols can contain a fairly large percentage (up
to 40% by weight) of paraffinic compounds which can be removed before the
reaction if desired.
Another example of a commercially available alcohol mixture is Adol 60
which comprises about 75% by weight of a straight chain C.sub.22 primary
alcohol, about 15% of a C.sub.20 primary alcohol and about 8% of C.sub.18
and C.sub.24 alcohols. Adol 320 comprises predominantly oleyl alcohol. The
Adol alcohols are marketed by Ashland Chemical.
A variety of mixtures of monohydric fatty alcohols derived from naturally
occurring triglycerides and ranging in chain length of from C.sub.8 to
C.sub.18 are available from Proctor & Gamble Company. These mixtures
contain various amounts of fatty alcohols containing mainly 12, 14, 16, or
18 carbon atoms. For example, CO-1214 is a fatty alcohol mixture
containing 0.5% of C.sub.10 alcohol, 66.0% of C.sub.12 alcohol, 26.0% of
C.sub.14 alcohol and 6.5% of C.sub.16 alcohol.
Another group of commercially available mixtures include the "Neodol"
products available from Shell Chemical Co. For example, Neodol 23 is a
mixture of C.sub.12 and C.sub.13 alcohols; Neodol 25 is a mixture of
C.sub.12 and C.sub.15 alcohols; and Neodol 45 is a mixture of C.sub.14 to
C.sub.15 linear alcohols. Neodol 91 is a mixture of C.sub.9, C.sub.10 and
C.sub.11 alcohols.
Fatty vicinal diols also are useful and these include those available from
Ashland Oil under the general trade designation Adol 114 and Adol 158. The
former is derived from a straight chain alpha olefin fraction of C.sub.11
-C.sub.14, and the latter is derived from a C.sub.15 -C.sub.18 fraction.
The amines that can be used in making the compounds of Formulae (A-I),
(A-II)or (A-III) may be primary, secondary or tertiary amines, or mixtures
thereof. Hydrocarbyl groups of the amines may be aliphatic, cycloaliphatic
or aromatic. These include alkyl and alkenyl groups. In one embodiment the
amine is an alkylamine wherein the alkyl group contains from 1 to about 50
carbon atoms, and in one embodiment 1 to about 30 carbon atoms, and in one
embodiment 1 to about 18 carbon atoms, and in one embodiment 1 to about 12
carbon atoms, and in one embodiment 1 to about 8 carbon atoms.
In one embodiment, the amines are primary hydrocarbyl amines containing
from about 2 to about 30, and in one embodiment about 4 to about 20 carbon
atoms in the hydrocarbyl group. The hydrocarbyl group may be saturated or
unsaturated. Representative examples of primary saturated amines are the
alkylamines such as methylamine, n-butylamine, n-hexylamine; those known
as aliphatic primary fatty amines, for example, the commercially known
"Armeen" primary amines (products available from Akzo Chemicals, Chicago,
Ill.). Typical fatty amines include amines such as, n-octylamine,
n-dodecylamine, n-etradecylamine, n-octadecylamine (stearylamine),
octadecenylamine (oleylamine), etc. Also suitable are mixed fatty amines
such as Akzo's Armeen-C, Armeen-O, Armeen-OD, Armeen-T, Armeen-HT, Armeen
S and Armeen SD, all of which are fatty amines of varying purity.
In one embodiment, the amine is a tertiary-aliphatic primary amine having
from about 4 to about 30, and in one embodiment about 6 to about 24, and
in one embodiment about 8 to about 24 carbon atoms in the aliphatic group.
Usually the tertiary-aliphatic primary amines are monoamines, and in one
embodiment alkylamines represented by the formula
##STR7##
wherein R is a hydrocarbyl group containing from 1 to about 30 carbon
atoms. Such amines are illustrated by tertiary-butylamine,
1-methyl-1-amino-cyclohexane, tertiary-octyl primary amine,
tertiary-tetradecyl primary amine, tertiary-hexadecyl primary amine,
tertiary-octadecyl primary amine, tertiary-octacosanyl primary amine.
Mixtures of tertiary alkyl primary amines are also useful for the purposes
of this invention. Illustrative of amine mixtures of this type are
"Primene 81R" which is a mixture of C.sub.11-14 tertiary alkyl primary
amines and "Primene JMT" which is a similar mixture of C.sub.18-22
tertiary alkyl primary amines (both are available from Rohm and Haas). The
tertiary alkyl primary amines and methods for their preparation are known
to those of ordinary skill in the art. The tertiary-alkyl primary amine
useful for the purposes of this invention and methods for their
preparation are described in U.S. Pat. No. 2,945,749 which is hereby
incorporated by reference for its teachings in this regard.
Primary amines in which the hydrocarbyl group comprises olefinic
unsaturation also are useful. Thus, the hydrocarbyl groups may contain one
or more olefinic unsaturation depending on the length of the chain,
usually no more than one double bond per 10 carbon atoms. Representative
amines are dodecenylamine, oleylamine and linoleylamine. Such unsaturated
amines are available under the Armeen tradename.
Secondary amines include dialkylamines having two of the above hydrocarbyl,
preferably alkyl or alkenyl groups described for primary amines including
such commercial fatty secondary amines as Armeen 2C and Armeen HT, and
also mixed dialkylamines wherein, for example, one alkyl group is a fatty
group and the other alkyl group may be a lower alkyl group (1-7 carbon
atoms) such as ethyl, butyl, etc., or the other hydrocarbyl group may be
an alkyl group bearing other non-reactive or polar substituents (CN,
alkyl, carbalkoxy, amide, ether, thioether, halo, sulfoxide, sulfone) such
that the essentially hydrocarbon character of the group is not destroyed.
Tertiary amines such as trialkyl or trialkenyl amines and those containing
a mixture of alkyl and alkenyl amines are useful. The alkyl and alkenyl
groups are substantially as described above for primary and secondary
amines.
Other useful primary amines are the primary etheramines represented by the
formula R"OR'NH.sub.2 wherein R' is a divalent alkylene group having 2 to
about 6 carbon atoms and R" is a hydrocarbyl group of about 5 to about 150
carbon atoms. These primary etheramines are generally prepared by the
reaction of an alcohol R"OH wherein R" is as defined hereinabove with an
unsaturated nitrile. Typically, the alcohol is a linear or branched
aliphatic alcohol with R" having up to about 50 carbon atoms, and in one
embodiment up to about 26 carbon atoms, and in one embodiment from about 6
to about 20 carbon atoms. The nitrile reactant can have from about 2 to
about 6 carbon atoms, with acrylonitrile being useful. Etheramines are
commercially available under the name SURFAM marketed by Mars Chemical
Company, Atlanta, Ga. Typical of such amines are those having a molecular
weight of from about 150 to about 400. Useful etheramines are exemplified
by those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A
(linear C.sub.16), SURFAM P17B (tridecyloxypropylamine). The hydrocarbyl
chain lengths (i.e., C.sub.14, etc.) of the SURFAM described above and
used hereinafter are approximate and include the oxygen ether linkage. For
example, a C.sub.14 SURFAM amine would have the following general formula
C.sub.10 H.sub.21 OC.sub.3 H.sub.6 NH.sub.2
The amines may be hydroxyamines. In one embodiment, these hydroxyamines can
be represented by the formula
##STR8##
wherein R.sup.1 is a hydrocarbyl group generally containing from about 6
to about 30 carbon atoms, R.sup.2 is an ethylene or propylene group,
R.sup.3 is an alkylene group containing up to about 5 carbon atoms, a is
zero or one, each R.sup.4 is hydrogen or a lower alkyl group, and x, y and
z are each independently integers from zero to about 10, at least one of
x, y and z being at least 1. The above hydroxyamines can be prepared by
techniques well known in the art, and many such hydroxyamines are
commercially available. Useful hydroxyamines where in the above formula a
is zero include 2-hydroxyethylhexylamine, 2-hydroxyethyloleylamine,
bis(2-hydroxyethyl)hexylamine, bis(2-hydroxyethyl)oleylamine, and mixtures
thereof. Also included are the comparable members wherein in the above
formula at least one of x and y is at least 2.
A number of hydroxyamines wherein a is zero are available from Armak under
the general trade designation "Ethomeen" and "Propomeen." Specific
examples include "Ethomeen C/15" which is an ethylene oxide condensate of
a coconut fatty amine containing about 5 moles of ethylene oxide;
"Ethomeen C/20" and "C/25" which also are ethylene oxide condensation
products from coconut fatty amine containing about 10 and 15 moles of
ethylene oxide, respectively. "Propomeen O/12" is the condensation product
of one mole of oleylamine with 2 moles propylene oxide.
Commercially available examples of alkoxylated amines where a is 1 include
"Ethoduomeen T/13" and "T/20" which are ethylene oxide condensation
products of N-tallow trimethylenediamine containing 3 and 10 moles of
ethylene oxide per mole of diamine, respectively.
The fatty diamines include mono- or dialkyl, symmetrical or asymmetrical
ethylenediamines, propanediamines (1,2 or 1,3) and polyamine analogs of
the above. Suitable fatty polyamines such as those sold under the name
Duomeen are commercially available diamines described in Product Data
Bulletin No. 7-10R.sub.1 of Armak. In another embodiment, the secondary
amines may be cyclic amines such as piperidine, piperazine, morpholine,
etc.
Also included as useful amines are the following:
(1) polyalkylenepolyamines of the general formula
(R).sub.2 --N--(U--NR).sub.n --R
wherein each R is independently a hydrogen atom or a hydrocarbyl group or a
hydroxy-substituted hydrocarbyl group containing up to about 30 carbon
atoms, with the proviso that at least one R is a hydrogen atom, n is a
number of 1 to about 10, and U is an alkylene group containing 1 to about
18 carbon atoms;
(2) heterocyclic-substituted polyamines including hydroxyalkyl-substituted
polyamines wherein the polyamines are as described above and the
heterocyclic substituent is, e.g., a piperazine, an imidazoline, a
pyrimidine, a morpholine, etc.; and
(3) aromatic polyamines of the general formula
Ar--(NR.sub.2).sub.y
wherein Ar is an aromatic nucleus of 6 to about 20 carbon atoms, each R is
independently a hydrogen atom or a hydrocarbyl group or a
hydroxy-substituted hydrocarbyl group containing up to about 30 carbon
atoms, with proviso that at least one R.sup.3 is a hydrogen atom, and y is
2 to about 8. Specific examples of the polyalkylenepolyamines (1) are
ethylenediamine, tetra(ethylene)pentamine, tri-(trimethylene)tetramine,
1,2-propylenediamine, etc. Specific examples of hydroxyalkyl-substituted
polyamines include N-(2-hydroxyethyl) ethylenediamine, N, N.sup.1
-bis(2-hydroxyethyl) ethylenediamine, N-(3-hydroxybutyl)
tetramethylenediamine, etc. Specific examples of the
heterocyclic-substituted polyamines (2) are N-2-aminoethylpiperazine, N-2
and N-3 aminopropylmorpholine, N-3-(dimethyl amino)propylpiperazine,
2-heptyl-3-(2-aminopropyl)imidazoline, 1,4-bis(2-aminoethyl)piperazine,
1-(2-hydroxyethyl)piperazine, and
2-heptadecyl-1-(2-hydroxyethyl)-imidazoline, etc. Specific examples of the
aromatic polyamines (3) are the various isomeric phenylenediamines, the
various isomeric naphthalenediamines, etc.
The dimercaptothiadiazoles which can be utilized in making the compounds
represented by Formulae (A-II)and (A-III) have the following structural
formulae and names.
##STR9##
These compounds are known in the art. Of these the most readily available,
and the one preferred for the purposes of this invention, is
2,5-dimercapto-1,3,4-thiadiazole. This compound can be prepared by the
reaction of one mole of hydrazine, or a hydrazine salt, with two moles of
carbon disulfide in an alkaline medium, followed by acidification.
The following examples illustrate the preparation of the mixed polysulfides
(A) that are useful with this invention. In the following examples as well
as throughout the specification and in the claims, unless otherwise
indicated, all parts and percentages are by weight, all temperatures are
in degrees Celsius, and the pressures are atmospheric.
EXAMPLE A-1
The following ingredients are charged to a reactor: 2 moles (80 grams) of
NaOH; 80 grams of distilled water; and 1 mole (74 grams) of n-butanol. 1.1
moles (84 grams) of carbon disulfide are added dropwise over 30 minutes.
One equivalent (346 grams) of dimethypentyl dithiophosphoric acid is added
dropwise. The reaction mixture exotherms. The mixture is stirred for 30
minutes. The mixture is cooled in a cold water bath and 2 moles (200
grams) of a 34% hydrogen peroxide solution are added dropwise over 4
hours. The mixture exotherms. The mixture contains an organic layer and an
aqueous/solids layer. The organic layer is separated from the
aqueous/solids layer. The aqueous/solids layer is washed with 200 ml. of
toluene three times to extract product in the form of a toluene extract
from the aqueous/solids layer. The organic layer and the toluene extract
are combined, stripped on a rotary evaporator at 20 mm Hg and 110.degree.
C., and filtered to provide the desired disulfide product.
EXAMPLE A-2
The following ingredients are charged to a reactor: 2 moles (80 grams) of
NaOH; 80 grams of distilled water; and 1 mole (129 grams) of
di-n-butylamine. 1.1 moles (84 grams) of carbon disulfide are added
dropwise over 30 minutes. One equivalent (346 grams) of dimethypentyl
dithiophosphoric acid is added dropwise. The reaction mixture exotherms.
The mixture is stirred for 30 minutes. The mixture is cooled in a cold
water bath and 2 moles (200 grams) of a 34% hydrogen peroxide solution are
added dropwise over 4 hours. The mixture exotherms. The mixture contains
an organic layer and an aqueous/solids layer. The organic layer is
separated from the aqueous/solids layer. The aqueous/solids layer is
washed with 200 ml. of toluene three times to extract product in the form
of a toluene extract from the aqueous/solids layer. The organic layer and
the toluene extract are combined, stripped on a rotary evaporator at 20
mm. Hg and 110.degree. C., and filtered to provide the desired disulfide
product.
EXAMPLE A-3
The following ingredients are charged to a reactor: 2 moles (80 grams) of
NaOH; 80 grams of distilled water; and 1 mole (74 grams) of 1-butanethiol.
1.1 moles (84 grams) of carbon disulfide are added dropwise over 30
minutes with stirring. One equivalent (346 grams) of dimethypentyl
dithiophosphoric acid is added dropwise. The reaction mixture exotherms.
The mixture is stirred for 30 minutes. The mixture is cooled in a cold
water bath and 2 moles (200 grams) of a 34% hydrogen peroxide solution are
added dropwise over 4 hours. The mixture exotherms. The mixture contains
an organic layer and an aqueous/solids layer. The organic layer is
separated from the aqueous/solids layer. The aqueous/solids layer is
washed with 200 ml. of toluene three times to extract product in the form
of a toluene extract from the aqueous/solids layer. The organic layer and
the toluene extract are combined, stripped on a rotary evaporator at 2 mm.
Hg and 110.degree. C., and filtered to provide the desired disulfide
product.
EXAMPLE A-4
A phosphorodithioic acid derived from P.sub.2 S.sub.5 and an alcohol
mixture of 40% by weight isopropyl alcohol and 60% by weight
4-methyl-secondary-amyl alcohol (305 grams, 1.0 equivalent) and
2,5-dimercapto-1,3,4-thiadiazole (75 grams, 0.5 equivalents) are charged
to a reactor. A 34% aqueous hydrogen peroxide solution (110 grams, 1.1
equivalents) is added dropwise while maintaining the temperature of the
reaction mixture at 78-100.degree. C. The reaction mixture is allowed to
stand and the mixture separates into two layers. The aqueous layer is
drawn off and the remaining organic layer is stripped at 110.degree. C.
and 20 mm Hg for two hours. The stripped organic layer is filtered using a
filter aid to provide the desired product which is in the form of a yellow
liquid.
EXAMPLE A-5
A phosphorodithioic acid derived from P.sub.2 S.sub.5 and ethyl hexyl
alcohol (400 grams, 1.02 equivalents) and 2,5-dimercapto-1,3,4-thiadiazole
(30.6 grams, 0.3 equivalent) are charged to a reactor. A 34% aqueous
hydrogen peroxide solution (75 grams, 0.75 equivalents) is added while
permitting the reaction mixture to reach its reflux temperature
(100.degree. C.). The mixture is stripped at 100.degree. C. and 20 mm Hg
and filtered to provide the desired disulfide product which is in the form
of a yellow liquid.
(B) Acylated Nitrogen-Containing Compounds
In one embodiment, the inventive composition further comprises an acylated
nitrogen-containing compound having a substituent of at least about 10
aliphatic carbon atoms. These compounds typically function as ashless
dispersants in lubricating compositions.
A number of acylated, nitrogen-containing compounds having a substituent of
at least about 10 aliphatic carbon atoms and made by reacting a carboxylic
acid acylating agent with an amino compound are known to those skilled in
the art. In such compositions the acylating agent is linked to the amino
compound through an imido, amido, amidine or salt linkage. The substituent
of at least about 10 aliphatic carbon atoms may be in either the
carboxylic acid acylating agent derived portion of the molecule or in the
amino compound derived portion of the molecule. Preferably, however, it is
in the acylating agent portion. The acylating agent can vary from formic
acid and its acyl derivatives to acylating agents having high molecular
weight aliphatic substituents of up to about 5,000, 10,000 or 20,000
carbon atoms. The amino compounds are characterized by the presence within
their structure of at least one HN< group.
In one embodiment, the acylating agent will be a mono- or polycarboxylic
acid (or reactive equivalent thereof) such as a substituted succinic or
propionic acid and the amino compound is a polyamine or mixture of
polyamines, most typically, a mixture of ethylene polyamines. The amine
also may be a hydroxyalkyl-substituted polyamine. The aliphatic
substituent in such acylating agents typically averages at least about 30
or at least about 50 and up to about 400 carbon atoms.
Illustrative hydrocarbon based groups containing at least 10 carbon atoms
are n-decyl, n-dodecyl, tetrapropylene, n-octadecyl, oleyl,
chlorooctadecyl, triicontanyl, etc. Generally, the hydrocarbon-based
substituents are made from homo- or interpolymers (e.g., copolymers,
terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as
ethylene, propylene, 1-butene, isobutene, butadiene, isoprene, 1-hexene,
1-octene, etc. Typically, these olefins are 1-monoolefins. The substituent
can also be derived from the halogenated (e.g., chlorinated or brominated)
analogs of such homo- or interpolymers. The substituent can, however, be
made from other sources, such as monomeric high molecular weight alkenes
(e.g., 1-tetracontene) and chlorinated analogs and hydrochlorinated
analogs thereof, aliphatic petroleum fractions, particularly paraffin
waxes and cracked and chlorinated analogs and hydrochlorinated analogs
thereof, white oils, synthetic alkenes such as those produced by the
Ziegler-Natta process (e.g., poly(ethylene) greases) and other sources
known to those skilled in the art. Any unsaturation in the substituent may
be reduced or eliminated by hydrogenation according to procedures known in
the art.
The hydrocarbon-based substituents are substantially saturated, that is,
they contain no more than one carbon-to carbon unsaturated bond for every
ten carbon-to-carbon single bonds present. Usually, they contain no more
than one carbon-to-carbon non-aromatic unsaturated bond for every 50
carbon-to-carbon bonds present.
The hydrocarbon-based substituents are also substantially aliphatic in
nature, that is, they contain no more than one non-aliphatic moiety
(cycloalkyl, cycloalkenyl or aromatic) group of 6 or less carbon atoms for
every 10 carbon atoms in the substituent. Usually, however, the
substituents contain no more than one such non-aliphatic group for every
50 carbon atoms, and in many cases, they contain no such non-aliphatic
groups at all; that is, the typical substituents are purely aliphatic.
Typically, these purely aliphatic substituents are alkyl or alkenyl
groups.
Specific examples of the substantially saturated hydrocarbon- based
substituents containing an average of more than 30 carbon atoms are the
following:
a mixture of poly(ethylene/propylene) groups of about 35 to about 70 carbon
atoms
a mixture of the oxidatively or mechanically degraded
poly(ethylene/propylene) groups of about 35 to about 70 carbon atoms
a mixture of poly(propylene/1-hexene) groups of about 80 to about 150
carbon atoms
a mixture of poly(isobutene) groups having an average of about 50 to about
200 carbon atoms
A useful source of the substituents are poly(isobutene)s obtained by
polymerization of a C.sub.4 refinery stream having a butene content of
about 35 to about 75 weight percent and isobutene content of about 30 to
about 60 weight percent in the presence of a Lewis acid catalyst such as
aluminum trichloride or boron trifluoride. These polybutenes contain
predominantly (greater than 80% of total repeating units) isobutene
repeating units of the configuration
##STR10##
In one embodiment, the carboxylic acid acylating agent is a hydrocarbon
substituted succinic acid or anhydride. The substituted succinic acid or
anhydride consists of hydrocarbon-based substituent groups and succinic
groups wherein the substituent groups are derived from a polyalkene, said
acid or anhydride being characterized by the presence within its structure
of an average of at least about 0.9 succinic group for each equivalent
weight of substituent groups, and in one embodiment about 0.9 to about 2.5
succinic groups for each equivalent weight of substituent groups. The
polyalkene generally has an (Mn) of at least about 700, and in one
embodiment about 700 to about 2000, and in one embodiment about 900 to
about 1800. The ratio between the weight average molecular weight (Mw) and
the (Mn) (that is, the Mw/Mn) can range from about 1 to about 10, or about
1.5 to about 5. In one embodiment the polyalkene has an Mw/Mn value of
about 2.5 to about 5. For purposes of this invention, the number of
equivalent weights of substituent groups is deemed to be the number
corresponding to the quotient obtained by dividing the Mn value of the
polyalkene from which the substituent is derived into the total weight of
the substituent groups present in the substituted succinic acid. Thus, if
a substituted succinic acid is characterized by a total weight of
substituent group of 40,000 and the Mn value for the polyalkene from which
the substituent groups are derived is 2000, then that substituted succinic
acylating agent is characterized by a total of 20 (40,000/2000=20)
equivalent weights of substituent groups.
In one embodiment the carboxylic acid acylating agent is a substituted
succinic acid or anhydride, said substituted succinic acid or anhydride
consisting of hydrocarbon-based substituent groups and succinic groups
wherein the substituent groups are derived from polybutene in which at
least about 50% of the total units derived from butenes is derived from
isobutylene. The polybutene is characterized by an Mn value of about 1500
to about 2000 and an Mw/Mn value of about 3 to about 4. These acids or
anhydrides are characterized by the presence within their structure of an
average of about 1.5 to about 2.5 succinic groups for each equivalent
weight of substituent groups.
In one embodiment the carboxylic acid is at least one substituted succinic
acid or anhydride, said substituted succinic acid or anhydride consisting
of substituent groups and succinic groups wherein the substituent groups
are derived from polybutene in which at least about 50% of the total units
derived from butenes is derived from isobutylene. The polybutene has an Mn
value of about 800 to about 1200 and an Mw/Mn value of about 2 to about 3.
The acids or anhydrides are characterized by the presence within their
structure of an average of about 0.9 to about 1.2 succinic groups for each
equivalent weight of substituent groups.
The amino compound is characterized by the presence within its structure of
at least one HN< group and can be a monoamine or polyamine. Mixtures of
two or more amino compounds can be used in the reaction with one or more
acylating reagents. In one embodiment, the amino compound contains at
least one primary amino group (i.e., --NH.sub.2) and more preferably the
amine is a polyamine, especially a polyamine containing at least two
--NH-- groups, either or both of which are primary or secondary amines.
The amines may be aliphatic, cycloaliphatic, aromatic or heterocyclic
amines.
Among the useful amines are the alkylene polyamines, including the
polyalkylene polyamines. The alkylene polyamines include those conforming
to the formula
RRN--(U--NR).sub.n--R
wherein n is from 1 to about 10; each R is independently a hydrogen atom, a
hydrocarbyl group or a hydroxy-substituted or amine-substituted
hydrocarbyl group having up to about 30 atoms, or two R groups on
different nitrogen atoms can be joined together to form a U group, with
the proviso that at least one R group is a hydrogen atom and U is an
alkylene group of about 2 to about 10 carbon atoms. Preferably, U is
ethylene or propylene. Especially preferred are the alkylene polyamines
where each R is hydrogen or an amino-substituted hydrocarbyl group with
the ethylene polyamines and mixtures of ethylene polyamines being the most
preferred. Usually n will have an average value of from about 2 to about
7. Such alkylene polyamines include methylene polyamine, ethylene
polyamines, propylene polyamines, butylene polyamines, pentylene
polyamines, hexylene polyamines, heptylene polyamines, etc. The higher
homologs of such amines and related amino alkyl-substituted piperazines
are also included.
Alkylene polyamines that are useful include ethylene diamine, triethylene
tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine,
decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine,
tripropylene tetramine, tetraethylene pentamine, trimethylene diamine,
pentaethylene hexamine, di(trimethylene)triamine,
N-(2-aminoethyl)piperazine, 1,4-bis(2-aminoethyl) piperazine, and the
like. Higher homologs as are obtained by condensing two or more of the
above-illustrated alkylene amines are useful, as are mixtures of two or
more of any of the afore-described polyamines.
Ethylene polyamines, such as those mentioned above, are especially useful
for reasons of cost and effectiveness. Such polyamines are described in
detail under the heading "Diamines and Higher Amines" in The Encyclopedia
of Chemical Technology, Second Edition, Kirk and Othmer, Volume 7, pages
27-39, Interscience Publishers, Division of John Wiley and Sons, 1965,
which is hereby incorporated by reference for the disclosure of useful
polyamines. Such compounds are prepared most conveniently by the reaction
of an alkylene chloride with ammonia or by reaction of an ethylene imine
with a ring-opening reagent such as ammonia, etc. These reactions result
in the production of the somewhat complex mixtures of alkylene polyamines,
including cyclic condensation products such as piperazines. These mixtures
can be used.
Other useful types of polyamine mixtures are those resulting from stripping
of the above-described polyamine mixtures. In this instance, lower
molecular weight polyamines and volatile contaminants are removed from an
alkylene polyamine mixture to leave as residue what is often termed
"polyamine bottoms". In general, alkylene polyamine bottoms can be
characterized as having less than two, usually less than 1% (by weight)
material boiling below about 200.degree. C. In the instance of ethylene
polyamine bottoms, which are readily available and found to be quite
useful, the bottoms contain less than about 2% (by weight) total
diethylene triamine (DETA) or triethylene tetramine (TETA). A typical
sample of such ethylene polyamine bottoms obtained from the Dow Chemical
Company of Freeport, Tex. designated "E-100" showed a specific gravity at
15.6.degree. C. of 1.0168, a percent nitrogen by weight of 33.15 and a
viscosity at 40.degree. C. of 121 centistokes. Gas chromatography analysis
of such a sample showed it to contain about 0.93% "Light Ends" (most
probably DETA), 0.72% TETA, 21.74% tetraethylene pentamine and 76.61 %
pentaethylene hexamine and higher (by weight). These alkylene polyamine
bottoms include cyclic condensation products such as piperazine and higher
analogs of diethylenetriamine, triethylenetetramine and the like.
These alkylene polyamine bottoms can be reacted solely with the acylating
agent, in which case the amino reactant consists essentially of alkylene
polyamine bottoms, or they can be used with other amines and polyamines,
or alcohols or mixtures thereof. In these latter cases at least one amino
reactant comprises alkylene polyamine bottoms.
Other polyamines are described in, for example, U.S. Pat. Nos. 3,219,666
and 4,234,435, and these patents are hereby incorporated by reference for
their disclosures of amines which can be reacted with the acylating agents
described above to form the acylated nitrogen-containing compounds (B) of
this invention.
In one embodiment, the amine may be a hydroxyamine. Typically, the
hydroxyamines are primary, secondary or tertiary alkanol amines or
mixtures thereof. Such amines can be represented by the formulae:
H.sub.2 N--R--OH RN(H)--R--OH RRN--R--OH
wherein each R is independently a hydrocarbyl group of one to about eight
carbon atoms or hydroxyhydrocarbyl group of two to about eight carbon
atoms, preferably one to about four, and R is a divalent hydrocarbyl group
of about two to about 18 carbon atoms, preferably two to about four. The
group --R --OH in such formulae represents the hydroxyhydrocarbyl group. R
can be an acyclic, alicyclic or aromatic group. Typically, R is an acyclic
straight or branched alkylene group such as an ethylene, 1,2-propylene,
1,2-butylene, 1,2-octadecylene, etc. group. Where two R groups are present
in the same molecule they can be joined by a direct carbon-to-carbon bond
or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-,
6-, 7- or 8-membered ring structure. Examples of such heterocyclic amines
include N-(hydroxyl lower alkyl)-morpholines, -thiomorpholines,
-piperidines, -oxazolidines, -thiazolidines and the like. Typically,
however, each R.sub.1 is independently a methyl, ethyl, propyl, butyl,
pentyl or hexyl group.
Examples of these alkanolamines include mono-, di-, and triethanol amine,
diethylethanolamine, ethylethanolamine, butyidiethanolamine, etc.
The hydroxyamines can also be an ether N-(hydroxyhydrocarbyl)-amine. These
are hydroxypoly(hydrocarbyloxy) analogs of the above-described hydroxy
amines (these analogs also include hydroxyl-substituted oxyalkylene
analogs). Such N-(hydroxyhydrocarbyl) amines can be conveniently prepared
by reaction of epoxides with afore-described amines and can be represented
by the formulae:
N.sub.2 N--(RO).sub.x --HRN(H)--(RO).sub.x H RRN--(RO).sub.x H
wherein x is a number from about 2 to about 15 and R and R are as described
above. R may also be a hydroxypoly(hydrocarbyloxy) group.
The acylated nitrogen-containing compounds (B) include amine salts, amides,
imides, amidines, amidic acids, amidic salts and imidazolines as well as
mixtures thereof. To prepare the acylated nitrogen-containing compounds
from the acylating reagents and the amino compounds, one or more acylating
reagents and one or more amino compounds are heated, optionally in the
presence of a normally liquid, substantially inert organic liquid solvent
diluent, at temperatures in the range of about 80.degree. C. up to the
decomposition point of either the reactants or the carboxylic derivative
but normally at temperatures in the range of about 100.degree. C. up to
about 300.degree. C. provided 300.degree. C. does not exceed the
decomposition point. Temperatures of about 125.degree. C. to about
250.degree. C. are normally used. The acylating reagent and the amino
compound are reacted in amounts sufficient to provide from about one-half
equivalent up to about 2 moles of amino compound per equivalent of
acylating reagent.
Many patents have described useful acylated nitrogen-containing compounds
including U.S. Pat. Nos. 3,172,892; 3,219,666; 3,272,746; 3,310,492;
3,341,542; 3,444,170; 3,455,831; 3,455,832; 3,576,743; 3,630,904;
3,632,511; 3,804,763; and 4,234,435. A typical acylated
nitrogen-containing compound of this class is that made by reacting a
poly(isobutene)-substituted succinic acid acylating agent (e.g.,
anhydride, acid, ester, etc.) wherein the poly(isobutene) substituent has
between about 50 to about 400 carbon atoms with a mixture of
ethylenepolyamines having about 3 to about 7 amino nitrogen atoms per
ethylenepolyamine and about 1 to about 6 ethylene units made from
condensation of ammonia with ethylene chloride. The above-noted U.S.
patents are hereby incorporated by reference for their disclosure of
acylated amino compounds and their method of preparation.
Another type of acylated nitrogen compound belonging to this class is that
made by reacting a carboxylic acid acylating agent with a polyamine,
wherein the polyamine is the product made by condensing a hydroxy material
with an amine. These compounds are described in U.S. Pat. No. 5,053,152
which is incorporated herein by reference for its disclosure of such
compounds.
Another type of acylated nitrogen compound belonging to this class is that
made by reacting the afore described alkyleneimines with the
afore-described substituted succinic acids or anhydrides and aliphatic
monocarboxylic acids having from 2 to about 22 carbon atoms. In these
types of acylated nitrogen compounds, the mole ratio of succinic acid to
monocarboxylic acid ranges from about 1:0.1 to about 1:1. Typical of the
monocarboxylic acid are formic acid, acetic acid, dodecanoic acid,
butanoic acid, oleic acid, stearic acid, the commercial mixture of stearic
acid isomers known as isostearic acid, tall oil acid, etc. Such materials
are more fully described in U.S. Pat. Nos. 3,216,936 and 3,250,715 which
are hereby incorporated by reference for their disclosures in this regard.
Still another type of acylated nitrogen compound useful in making the
compositions of this invention is the product of the reaction of a fatty
monocarboxylic acid of about 12-30 carbon atoms and the afore-described
alkyleneamines, typically, ethylene-, propylene- or trimethylenepolyamines
containing 2 to 8 amino groups and mixtures thereof. The fatty
monocarboxylic acids are generally mixtures of straight and branched chain
fatty carboxylic acids containing 12-30 carbon atoms. A widely used type
of acylated nitrogen compound is made by reacting the afore-described
alkylenepolyamines with a mixture of fatty acids having from 5 to about 30
mole percent straight chain acid and about 70 to about 95% mole branched
chain fatty acids. Among the commercially available mixtures are those
known widely in the trade as isostearic acid. These mixtures are produced
as a by-product from the dimerization of unsaturated fatty acids as
described in U.S. Pat. Nos. 2,812,342 and 3,260,671.
The branched chain fatty acids can also include those in which the branch
is not alkyl in nature, such as found in phenyl and cyclohexyl stearic
acid and the chloro-stearic acids. Branched chain fatty carboxylic
acid/alkylene polyamine products have been described extensively in the
art. See for example, U.S. Pat. Nos. 3,110,673; 3,251,853; 3,326,801;
3,337,459; 3,405,064; 3,429,674; 3,468,639; 3,857,791. These patents are
hereby incorporated by reference for their disclosure of fatty
acid/polyamine condensates for use in lubricating oil formulations.
The following specific examples illustrate the preparation of exemplary
acylated nitrogen-containing compounds (B) useful with this invention.
EXAMPLE B-1
1000 parts by weight of polyisobutylene (Mn=1700) substituted succinic
anhydride and 1270 parts by weight of diluent oil are blended together and
heated to 110.degree. C. 59.7 parts by weight of a mixture of
polyethyleneamine bottoms and diethylenetriamine are added over a two-hour
period. The mixture exotherms to 121-132.degree. C. The mixture is heated
to 149.degree. C. with nitrogen blowing. The mixture is maintained at
149-154.degree. C. for one hour with nitrogen blowing. The mixture is then
filtered at 149.degree. C. Diluent oil is added to provide a mixture
having an oil content of 55% by weight.
EXAMPLE B-2
A blend of 800 parts by weight of polyisobutylene (Mn=940) substituted
succinic anhydride and 200 parts by weight of diluent oil is heated to
150.degree. C. with a nitrogen sparge. 87.2 parts by weight of
methylpentaerythritol are added over a one-hour period while maintaining
the temperature at 150-160.degree. C. The mixture is heated to 204.degree.
C. over a period of eight hours, and maintained at 204-210.degree. C. for
six hours. 15.2 parts by weight of a mixture of polyethyleneamine bottoms
and diethylenetriamine are added over a one-hour period while maintaining
the temperature of the mixture at 204-210.degree. C. 519.5 parts of
diluent oil are added to the mixture while maintaining the temperature at
a minimum of 177.degree. C. The mixture is cooled to 130.degree. C. and
filtered to provide the desired product.
(C) Phosphorus Compound.
The phosphorus compound (C) can be a phosphorus acid, ester or derivative
thereof. These include phosphorus acid, phosphorus acid ester, phosphorus
acid salt, or derivative thereof. The phosphorus acids include the
phosphoric, phosphonic, phosphinic and thiophosphoric acids including
dithiophosphoric acid as well as the monothiophosphoric, thiophosphinic
and thiophosphonic acids.
The phosphorus compound (C) can be a phosphorus acid ester derived from a
phosphorus acid or anhydride and an alcohol of 1 to about 50 carbon atoms,
and in one embodiment 1 to about 30 carbon atoms. It can be a phosphite, a
monothiophosphate, a dithiophosphate, or a dithiophosphate disulfide. It
can also be a metal, amine or ammonium salt of a phosphorus acid or
phosphorus acid ester. It can be a phosphorus containing amide or a
phosphorus-containing carboxylic ester.
The phosphorus compound can be a phosphate, phosphonate, phosphinate or
phosphine oxide. These compounds can be represented by the formula
##STR11##
wherein in Formula (C-I), R.sup.1, R.sup.2 and R.sup.3 are independently
hydrogen or hydrocarbyl groups, X is O or S, and a, b and c are
independently zero or 1. The phosphorus compound can be a phosphite,
phosphonite, phosphinite or phosphine. These compounds can be represented
by the formula
##STR12##
wherein in Formula (C-II), R.sup.1, R.sup.2 and R.sup.3 are independently
hydrogen or hydrocarbyl groups, and a, b and c are independently zero or
1.
The total number of carbon atoms in R.sup.1, R.sup.2 and R.sup.3 in each of
the above Formulae (C-I) and (C-II) must be sufficient to render the
compound soluble in the low-viscosity oil used in formulating the
inventive compositions. Generally, the total number of carbon atoms in
R.sup.1, R.sup.2 and R.sup.3 is at least about 8, and in one embodiment at
least about 12, and in one embodiment at least about 16. There is no limit
to the total number of carbon atoms in R.sup.1, R.sup.2 and R.sup.3 that
is required, but a practical upper limit is about 400 or about 500 carbon
atoms. In one embodiment, R.sup.1, R.sup.2 and R.sup.3 in each of the
above formulae are independently hydrocarbyl groups of 1 to about 100
carbon atoms, or 1 to about 50 carbon atoms, or 1 to about 30 carbon
atoms, with the proviso that the total number of carbons is at least about
8. Each R.sup.1, R.sup.2 and R.sup.3 can be the same as the other,
although they may be different. Examples of useful R.sup.1, R.sup.2 and
R.sup.3 groups include isopropyl, n-butyl, isobutyl, amyl,
4-methyl-2-pentyl, isooctyl, decyl, dodecyl, tetradecyl, 2-pentenyl,
dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, phenylalkyl,
naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl, and the like.
The phosphorus compounds represented by Formulae (C-I) and (C-II) can be
prepared by reacting a phosphorus acid or anhydride with an alcohol or
mixture of alcohols corresponding to R.sup.1, R.sup.2 and R.sup.3 in
Formulae (C-I) and (C-II). The phosphorus acid or anhydride is generally
an inorganic phosphorus reagent such as phosphorus pentoxide, phosphorus
trioxide, phosphorus tetraoxide, phosphorus acid, phosphorus halide, or
lower phosphorus esters, and the like. Lower phosphorus acid esters
contain from 1 to about 7 carbon atoms in each ester group. The phosphorus
acid ester may be a mono, di- or triphosphoric acid ester.
The phosphorus compound (C) can be a compound represented by the formula
##STR13##
wherein in Formula (C-III): X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are
independently oxygen or sulfur, and X.sub.1 and X.sup.2 can be NR.sup.4 ;
a and b are independently zero or one; R.sup.1, R.sup.2 R.sup.3 and
R.sup.4 are independently hydrocarbyl groups, and R.sup.3 and R.sup.4 can
be hydrogen.
Useful phosphorus compounds of the type represented by Formula (C-III) are
phosphorus- and sulfur-containing compounds. These include those compounds
wherein at least one X.sup.3 or X.sup.4 is sulfur, and in one embodiment
both X.sup.3 and X.sup.4 are sulfur, at least one X.sub.1 or X.sup.2 is
oxygen or sulfur, and in one embodiment both X.sub.1 and X.sup.2 are
oxygen, a and b are each 1, and R.sup.3 is hydrogen. Mixtures of these
compounds may be employed in accordance with this invention.
In Formula (C-III), R.sup.1 and R.sup.2 are independently hydrocarbyl
groups that are preferably free from acetylenic unsaturation and usually
also from ethylenic unsaturation and in one embodiment have from about 1
to about 50 carbon atoms, and in one embodiment from about 1 to about 30
carbon atoms, and in one embodiment from about 1 to about 18 carbon atoms,
and in one embodiment from about 1 to about 8 carbon atoms. Each R.sup.1
and R.sup.2 can be the same as the other, although they may be different
and either or both may be mixtures. Examples of R.sup.1 and R.sup.2 groups
include isopropyl, n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, isooctyl,
decyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl,
alkylphenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl,
alkylnaphth-lkyl, and mixtures thereof. Particular examples of useful
mixtures include, for example, isopropyl/n-butyl; isopropyl/secondary
butyl; isopropyl/4-methyl-2-pentyl; isopropyl/2-ethyl-1-hexyl;
isopropyl/isooctyl; isopropyl/decyl; isopropyl/dodecyl; and isopropyl
tridecyl.
In Formula (C-III), R.sup.3 and R.sup.4 are independently hydrogen or
hydrocarbyl groups (e.g. alkyl) of 1 to about 12 carbon atoms, and in one
embodiment 1 to about 4 carbon atoms. R.sup.3 is preferably hydrogen.
Phosphorus compounds corresponding to Formula (C-III) wherein X.sup.3 and
X.sup.4 are sulfur can be obtained by the reaction of phosphorus
pentasulfide (P.sub.2 S.sub.5) and an alcohol or mixture of alcohols
corresponding to R.sup.1 and R.sup.2. The reaction involves mixing at a
temperature of about 20.degree. C. to about 200.degree. C., four moles of
alcohol with one mole of phosphorus pentasulfide. Hydrogen sulfide is
liberated in this reaction. The oxygen-containing analogs of these
compounds can be prepared by treating the dithioic acid with water or
steam which, in effect, replaces one or both of the sulfur atoms.
In one embodiment, the phosphorus compound (C) is a monothiophosphoric acid
ester or a monothiophosphate. Monothiophosphates are prepared by the
reaction of a sulfur source and a dihydrocarbyl phosphite. The sulfur
source may be elemental sulfur, a sulfide, such as a sulfur coupled olefin
or a sulfur coupled dithiophosphate. Elemental sulfur is a useful sulfur
source. The preparation of monothiophosphates is disclosed in U.S. Pat.
No. 4,755,311 and PCT Publication WO 87/07638 which are incorporated
herein by reference for their disclosure of monothiophosphates, sulfur
sources for preparing monothiophosphates and the process for making
monothiophosphates.
Monothiophosphates may also be formed in the lubricant blend or functional
fluid by adding a dihydrocarbyl phosphite to a lubricating oil composition
or functional fluid containing a sulfur source. The phosphite may react
with the sulfur source under blending conditions (i.e., temperatures from
about 30.degree. C. to about 100.degree. C. or higher) to form the
monothiophosphate.
Useful phosphorus acid esters include those prepared by reacting a
phosphoric acid or anhydride with cresol alcohols. An example is tricresol
phosphate.
In one embodiment, the phosphorus compound (C) is a dithiophosphoric acid
or phosphorodithioic acid. The dithiophosphoric acid can be reacted with
an epoxide or a glycol to form an intermediate. The intermediate is then
reacted with a phosphorus acid, anhydride, or lower ester. The epoxide is
generally an aliphatic epoxide or a styrene oxide. Examples of useful
epoxides include ethylene oxide, propylene oxide, butene oxide, octene
oxide, dodecene oxide, styrene oxide, etc. Propylene oxide is useful. The
glycols may be aliphatic glycols having from 1 to about 12, and in one
embodiment about 2 to about 6, and in one embodiment 2 or 3 carbon atoms,
or aromatic glycols. Aliphatic glycols include ethylene glycol, propylene
glycol, triethylene glycol and the like. Aromatic glycols include
hydroquinone, catechol, resorcinol, and the like. These are described in
U.S. Pat. No. 3,197,405 which is incorporated herein by reference for its
disclosure of dithiophosphoric acids, glycols, epoxides, inorganic
phosphorus reagents and methods of reacting the same.
In one embodiment the phosphorus compound (C) is a phosphite. The phosphite
can be a di- or trihydrocarbyl phosphite. Each hydrocarbyl group can have
from 1 to about 24 carbon atoms, or from 1 to about 18 carbon atoms, or
from about 2 to about 8 carbon atoms. Each hydrocarbyl group may be
independently alkyl, alkenyl or aryl. When the hydrocarbyl group is an
aryl group, then it contains at least about 6 carbon atoms; and in one
embodiment about 6 to about 18 carbon atoms. Examples of the alkyl or
alkenyl groups include propyl, butyl, hexyl, heptyl, octyl, oleyl,
linoleyl, stearyl, etc. Examples of aryl groups include phenyl, naphthyl,
heptylphenol, etc. In one embodiment each hydrocarbyl group is
independently propyl, butyl, pentyl, hexyl, heptyl, oleyl or phenyl, more
preferably butyl, oleyl or phenyl and more preferably butyl or oleyl.
Phosphites and their preparation are known and many phosphites are
available commercially. Useful phosphites include dibutyl hydrogen
phosphite, trioleyl phosphite and triphenyl phosphite.
In one embodiment, the phosphorus compound (C) is a - phosphorus-containing
amide. The phosphorus-containing amides may be prepared by the reaction of
a phosphorus acid (e.g., a dithiophosphoric acid as described above) with
an unsaturated amide. Examples of unsaturated amides include acrylamide,
N,N -methylenebisacrylamide, methacrylamide, crotonamide, and the like.
The reaction product of the phosphorus acid with the unsaturated amide may
be further reacted with linking or coupling compounds, such as
formaldehyde or paraformaldehyde to form coupled compounds. The
phosphorus-containing amides are known in the art and are disclosed in
U.S. Pat. Nos. 4,876,374, 4,770,807 and 4,670,169 which are incorporated
by reference for their disclosures of phosphorus amides and their
preparation.
In one embodiment, the phosphorus compound (C) is a phosphorus-containing
carboxylic ester. The phosphorus-containing carboxylic esters may be
prepared by reaction of one of the above-described phosphorus acids, such
as a dithiophosphoric acid, and an unsaturated carboxylic acid or ester,
such as acrylic acid or a vinyl or allyl carboxylic acid or ester. If the
carboxylic acid is used, the ester may then be formed by subsequent
reaction with an alcohol.
The vinyl ester of a carboxylic acid may be represented by the formula
RCH.dbd.CH--O(O)CR.sup.1 wherein R is a hydrogen or hydrocarbyl group
having from 1 to about 30 carbon atoms, preferably hydrogen or a
hydrocarbyl group having 1 to about 12, more preferably hydrogen, and
R.sup.1 is a hydrocarbyl group having 1 to about 30 carbon atoms,
preferably 1 to about 12, more preferably 1 to about 8. Examples of vinyl
esters include vinyl acetate, vinyl 2-ethylhexanoate, vinyl butanoate, and
vinyl crotonate.
In one embodiment, the unsaturated carboxylic ester is an ester of an
unsaturated carboxylic acid, such as maleic, fumaric, acrylic,
methacrylic, itaconic, citraconic acids and the like. The ester can be
represented by the formula RO--(O)C--HC.dbd.CH--C(O)OR wherein each R is
independently a hydrocarbyl group having 1 to about 18 carbon atoms, or 1
to about 12, or 1 to about 8 carbon atoms. Examples of unsaturated
carboxylic esters that are useful include methylacrylate, ethylacrylate,
2-ethylhexylacrylate, 2-hydroxyethylacrylate, ethylmethacrylate,
2-hydroxy-ethylmethacrylate, 2-hydroxypropylmethacrylate,
2-hydroxypropylacrylate, ethylmaleate, butylmaleate and
2-ethylhexylmaleate. The above list includes mono- as well as diesters of
maleic, fumaric and citraconic acids.
In one embodiment, the phosphorus compound (C) is the reaction product of a
phosphorus acid and a vinyl ether. The vinyl ether is represented by the
formula R--CH.sub.2 .dbd.CH--OR.sup.1 wherein R is hydrogen or a
hydrocarbyl group having 1 to about 30, preferably 1 to about 24, more
preferably 1 to about 12 carbon atoms, and R.sup.1 is a hydrocarbyl group
having 1 to about 30 carbon atoms, preferably 1 to about 24, more
preferably 1 to about 12 carbon atoms. Examples of vinyl ethers include
vinyl methylether, vinyl propylether, vinyl 2-ethylhexylether and the
like.
When the phosphorus compound (C) is acidic, it may be reacted with an
ammonia or a source of ammonia, an amine, or metallic base to form the
corresponding salt. The salts may be formed separately and then added to
the lubricating oil or functional fluid composition. Alternatively, the
salts may be formed when the acidic phosphorus compound (C) is blended
with other components to form the lubricating oil or functional fluid
composition. The phosphorus compound can then form salts with basic
materials which are in the lubricating oil or functional fluid composition
such as basic nitrogen containing compounds (e.g., the above-discussed
acylated nitrogen-containing compounds (B)) and overbased materials.
The metal salts which are useful with this invention include those salts
containing Group IA, IIA or IIB metals, aluminum, lead, tin, iron,
molybdenum, manganese, cobalt, nickel or bismuth. Zinc is an especially
useful metal. These salts can be neutral salts or basic salts. Examples of
useful metal salts of phosphorus-containing acids, and methods for
preparing such salts are found in the prior art such as U.S. Pat. Nos.
4,263,150, 4,289,635; 4,308,154; 4,322,479; 4,417,990; and 4,466,895, and
the disclosures of these patents are hereby incorporated by reference.
These salts include the Group II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium
di(heptylphenyl)-phosphorodithioate, cadmium dinonylphosphorodithioate,
and the zinc salt of a phosphorodithioic acid produced by the reaction of
phosphorus pentasulfide with an equimolar mixture of isopropyl alcohol and
n-hexyl alcohol.
The following examples illustrate the preparation of useful metal salts of
the phosphorus compounds (C).
EXAMPLE C-1
(a) A mixture of 317.33 grams (5.28 moles) of 2-propanol and 359.67 grams
(3.52 moles) of 4-methyl-2-pentanol is prepared and heated to 60.degree.
C. Phosphorus pentasulfide (444.54 grams, 2.0 moles) is added to the
alcohol mixture while maintaining the temperature at 60.degree. C. Two
moles of hydrogen sulfide are liberated and trapped with a 50% aqueous
sodium hydroxide trap. The mixture is heated to and maintained at
70.degree. C. for two hours. The mixture is cooled to room temperature and
filtered through diatomaceous earth to yield a liquid green product having
an acid number in the range of 193-203.
(b) 89.1 grams (1.1 moles) of ZnO are added to 200 ml of toluene. 566.6
grams (2.0 equivalents based on acid number) of the product from part (a)
are added dropwise to the ZnO/toluene mixture. The resulting reaction is
exothermic. The reaction mixture is stripped to 70.degree. C. and 20 mm Hg
to remove water of reaction, toluene and excess alcohol. The residue is
filtered through diatomaceous earth. The filtrate, which is the desired
product, is a yellow viscous liquid.
EXAMPLE C-2
137.6 grams of zinc oxide are mixed with 149.9 grams of diluent oil. 17.7
grams of 2-ethylhexanoic acid are added. 1000 grams of a phosphorodithioic
acid derived from P.sub.2 S.sub.5 and 2-ethylhexanol are then added to the
mixture. The mixture is allowed to neutralize. It is then flash dried and
vacuum stripped. 81.1 grams of triphenyl phosphite are added. The
temperature of the mixture is adjusted to 124-129.degree. C. and
maintained at that temperature for three hours. The mixture is cooled to
room temperature and filtered using filter aid to provide the desired
product.
When the phosphorus compound (C) is an ammonium salt, the salt is
considered as being derived from ammonia (NH.sub.3) or an ammonia yielding
compound such as NH.sub.4 OH. Other ammonia yielding compounds will
readily occur to those skilled in the art.
When the phosphorus compound (C) is an amine salt, the salt may be
considered as being derived from amines. Any of the amines discussed above
under the subtitle "(B) Acylated Nitrogen-Containing Compounds" can be
used.
The following examples illustrate the preparation of amine or ammonium
salts of the phosphorus compounds (C) that can be used with this
invention.
EXAMPLE C-3
Phosphorus pentoxide (208 grams, 1.41 moles) is added at 50.degree. C. to
60.degree. C. to hydroxypropyl O,O'-diisobutylphosphorodithioate (prepared
by reacting 280 grams of propylene oxide with 1184 grams of
O,O'-di-isobutylphosphorodithioic acid at 30.degree. C. to 60.degree. C.).
The reaction mixture is heated to 80.degree. C. and held at that
temperature for 2 hours. To the acidic reaction mixture there is added a
stoichiometrically equivalent amount (384 grams) of a commercial aliphatic
primary amine at 30.degree. C. to 60.degree. C. The product is filtered.
The filtrate has a phosphorus content of 9.31%, a sulfur content of
11.37%, a nitrogen content of 2.50%, and a base number of 6.9 (bromphenol
blue indicator).
EXAMPLE C-4
(a) O,O-di-(2-ethylhexyl) dithiophosphoric acid (354 grams) having an acid
number of 154 is introduced into a stainless steel "shaker" type autoclave
of 1320 ml capacity having a thermostatically controlled heating jacket.
Propylene oxide is admitted until the pressure rises to 170 psig at room
temperature, and then the autoclave is sealed and shaken for 4 hours at
50.degree. C. to 100.degree. C. during which time the pressure rises to a
maximum of 550 psig. The pressure decreases as the reaction proceeds. The
autoclave is cooled to room temperature, the excess propylene oxide is
vented and the contents removed. The product (358 grams), a dark liquid
having an acid number of 13.4, is substantially
O,O-di-(2-ethylhexyl)-S-hydroxyisopropyl dithiophosphate.
(b) Ammonia is blown into the product of part (a) until a substantially
neutral product is obtained.
The phosphorus compound (C) can be a phosphorus-containing sulfide
represented by the formula
##STR14##
wherein in Formula (C-IV), R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently hydrocarbyl groups, X.sup.1 and X.sup.2 are independently O
or S, and n is zero to 3. In one embodiment X.sup.1 and X.sup.2 are each
S, and n is 1. R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently
hydrocarbyl groups that are preferably free from acetylenic unsaturation
and usually also free from ethylenic unsaturation. In one embodiment
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently have from about 1 to
about 50 carbon atoms, and in one embodiment from about 1 to about 30
carbon atoms, and in one embodiment from about 1 to about 18 carbon atoms,
and in one embodiment from about 1 to about 8 carbon atoms. Each R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 can be the same as the other, although they
may be different and mixtures may be used. Examples of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 groups include isopropyl, butyl, n-butyl, isobutyl,
amyl, 4-methyl-2-pentyl, octyl, isooctyl, decyl, dodecyl, tetradecyl,
2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl,
phenylalkyl, naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl, and
mixtures thereof.
The compounds represented by Formula (C-IV) can be prepared by first
reacting an alcohol, phenol or aliphatic or aromatic mercaptan with a
sulfide of phosphorus, such as P.sub.2 S.sub.3, P.sub.2 S.sub.5, P.sub.4
S.sub.3, P.sub.4 S.sub.7, P.sub.4 S.sub.10, and the like, to form a
partially esterified thiophosphorus or thiophosphoric acid, and then
further reacting this product as such or in the form of a metal salt with
an oxidizing agent or with a sulfur halide. Thus, when an alcohol is
reacted with phosphorus trisulfide, a dialkylated monothiophosphorus acid
is formed according to the following equation:
4ROH+P.sub.2 S.sub.3 .fwdarw.2(RO).sub.2 PSH+H.sub.2 S
This alkylated thiophosphorus acid may then be treated with an oxidizing
agent such as hydrogen peroxide or with sulfur dichloride or sulfur
monochloride to form a disulfide, trisulfide, or tetrasulfide,
respectively, according to the following equations:
##STR15##
Similarly, when the alcohol is reacted with phosphorus pentasulfide, the
corresponding di-substituted dithiophosphoric acid is formed, and this may
likewise be converted into disulfide, trisulfide or tetrasulfide
compounds. Suitable alcohols such as those discussed below may be
employed. Sulfurized alcohols such as sulfurized oleyl alcohol may also be
used. Corresponding reactions take place by starting with mercaptans,
phenols or thiophenols instead of alcohols. Suitable oxidizing agents for
converting the thiophosphorus and thiophosphoric acids to disulfides
include iodine, potassium triodide, ferric chloride, sodium hypochlorite,
hydrogen peroxide, oxygen, etc.
Alcohols used to prepare the phosphorus-containing sulfides of Formula
(C-IV) can be any of the alcohols described above under the subtitle "(A)
Mixed Polysulfides."
The following examples illustrate the preparation of phosphorus-containing
sulfides (C) represented by Formula (C-IV) that are useful with this
invention.
EXAMPLE C-5
A phosphorodithioic acid derived from P.sub.2 S.sub.5 and an alcohol
mixture of 40% by weight isopropyl alcohol and 60% by weight
4-methyl-secondary-amyl alcohol (4518 grams, 14.34 equivalents) is charged
to a reactor. A 30% aqueous hydrogen peroxide solution (1130 grams, 10.0
moles) is added dropwise at a rate of 7.3 grams per minute. The
temperature of the reaction mixture increases from 24.degree. C. to
38.degree. C. A 50% aqueous sodium hydroxide solution (40 grams, 0.50
equivalents) is added. The reaction mixture is stirred for 5 minutes, and
then allowed to stand. The mixture separates into two layers. The aqueous
layer contains water, phosphorodithioic acid salt and excess alcohol from
the phosphorodithioic acid. The organic layer contains the desired
product. The aqueous layer is drawn off (1108 grams) and the remaining
organic portion is stripped at 100.degree. C. and 20 mm Hg for two hours.
The stripped organic product is filtered using a filter aid to provide the
desired product which is a phosphorus-containing disulfide in the form of
a clear yellow liquid (4060 grams).
EXAMPLE C-6
A phosphorodithioic acid derived from 4-methyl-2-pentanol and P.sub.2
S.sub.5 (1202 grams, 3.29 equivalents) is charged to a reactor. A 30%
aqueous hydrogen peroxide solution (319 grams, 2.82 moles) is added
dropwise at a rate of 7.3 grams per minute. The temperature of the
reaction mixture increases from 24.degree. C. to 38.degree. C. A 50%
aqueous sodium hydroxide solution (12 grams, 0.15 equivalents) is added.
The reaction mixture is stirred for 5 minutes, and then allowed to stand.
The mixture separates into two layers. The aqueous layer contains water,
phosphorodithioic acid salt and excess methylamyl alcohol from the
phosphorodithioic acid. The organic layer contains the desired product.
The aqueous layer is drawn off and the remaining organic portion is
stripped at 100.degree. C. and 20 mm Hg for two hours. The stripped
organic product is filtered using filter aid to provide the desired
phosphorus-containing disulfide product which is a clear yellow liquid
(1016 grams).
EXAMPLE C-7
(a) A mixture of 105.6 grams (1.76 moles) of isopropyl alcohol and 269.3
grams (2.64 moles) of 4-methyl-2-pentanol is prepared and heated to
70.degree. C. Phosphorus pentasulfide (222 grams, 1 mole) is added to the
alcohol mixture while maintaining the temperature at 70.degree. C. One
mole of hydrogen sulfide is liberated. The mixture is maintained at
70.degree. C. for an additional four hours. The mixture is filtered
through diatomaceous earth to yield a green liquid product having an acid
number in the range of 179-189.
(b) 44.6 grams (1.09 equivalents) of ZnO are added to diluent oil to form a
slurry. One equivalent (based upon the measured acid number) of the
phosphorodithioic acid prepared in (a) are added dropwise to the ZnO
slurry. The reaction is exothermic. The reaction mixture is stripped to
100.degree. C. and 20 mm Hg to remove water of reaction and excess
alcohol. The residue is filtered through diatomaceous earth. The filtrate,
which is a viscous liquid, is diluted with diluent oil to provide a final
product having a 9.5% by weight phosphorus content.
(c) A mixture of the product of part (a) of this example (184 grams) and
part (b) (130 grams) is placed in a reactor. A 30% aqueous hydrogen
peroxide solution (80 grams) is added dropwise. After the hydrogen
peroxide addition is complete, the reaction mixture is stripped at
70.degree. C. and 20 mm Hg. The reaction mixture is filtered through
diatomaceous earth to provide the desired product which is in the form of
a yellow liquid.
(D) Thiocarbamate.
Component (D) is a thiocarbamate which can be represented by the formula
R.sup.1 R.sup.2 N--C(X)S--(CR.sup.3 R.sup.4).sub.a Z (D-I)
wherein in Formula (D-I), R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently hydrogen or hydrocarbyl groups, provided that at least one
of R.sup.1 or R.sup.2 is a hydrocarbyl group; X is O or S; a is 1 or 2;
and Z is a hydrocarbyl group, a hetero group (that is, a group attached
through a hetero atom such as O, N, or S), a hydroxy hydrocarbyl group, an
activating group, or a group represented by the formula
--(S)C(X)--NR.sup.1 R.sup.2.
When a is 2, Z is an activating group. In describing Z as an "activating
group," what is meant is a group which will activate an olefin to which it
is attached toward nucleophilic addition by, e.g., CS.sub.2 or COS derived
intermediates. (This is reflective of a method by which this material can
be prepared, by reaction of an activated olefin with CS.sub.2 and an
amine.) The activating group Z can be, for instance, an ester group,
typically but not necessarily a carboxylic ester group of the structure
--COOR.sup.5. It can also be an ester group based on a non-carbon acid,
such as a sulfonic or sulfinic ester or a phosphonic or phosphinic ester.
The activating group can also be any of the acids corresponding to the
aforementioned esters. Z can also be an amide group, that is, based on the
condensation of an acid group, preferably a carboxylic acid group, with an
amine. In that case the --(CR.sup.3 R.sup.4).sub.a Z group can be derived
from acrylamide. Z can also be an ether group, --OR.sup.5 ; a carbonyl
group, that is, an aldehyde or a ketone group; a cyano group, --CN, or an
aryl group. In one embodiment Z is an ester group of the structure,
--COOR.sup.5, where R.sup.5 is a hydrocarbyl group. R.sup.5 can comprise 1
to about 18 carbon atoms, and in one embodiment 1 to about 6 carbon atoms.
In one embodiment R.sup.5 is methyl so that the activating group is
--COOCH.sub.3.
When a is 1, Z need not be an activating group, because the molecule is
generally prepared by methods, described below, which do not involve
nucleophilic addition to an activated double bond.
When Z is a hydrocarbyl or a hydroxy hydrocarbyl group, a can be zero, 1 or
2. These hydrocarbyl groups can have from 1 to about 30 carbon atoms, and
in one embodiment 1 to about 18 carbon atoms, and in one embodiment 1 to
about 12 carbon atoms. Examples include methyl, ethyl, propyl, n-butyl,
isobutyl, pentyl, isopentyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl,
dodecyl, and the corresponding hydroxy-substituted hydrocarbyl groups such
as hydroxymethyl, hydroxyethyl, hydroxypropyl, etc.
R.sup.3 and R.sup.4 can be, independently, hydrogen or methyl or ethyl
groups. When a is 2, at least one of R.sup.3 and R.sup.4 is normally
hydrogen so that this compound will be R.sup.1 R.sup.2 N--C(S)S--CR.sup.3
HCR.sup.3 R.sup.4 COOR.sup.5. In one embodiment the thiocarbamate is
R.sup.1 R.sup.2 N--C(S)S--CH.sub.2 CH.sub.2 COOCH.sub.3. (These materials
can be derived from methyl methacrylate and methyl acrylate,
respectively.) These and other materials containing appropriate activating
groups are disclosed in greater detail in U.S. Pat. No. 4,758,362, which
is incorporated herein by reference.
The substituents R.sup.1 and R.sup.2 on the nitrogen atom are likewise
hydrogen or hydrocarbyl groups, but at least one should be a hydrocarbyl
group. It is generally believed that at least one such hydrocarbyl group
is desired in order to provide a measure of oil-solubility to the
molecule. However, R.sup.1 and R.sup.2 can both be hydrogen, provided the
other R groups in the molecule provide sufficient oil solubility to the
molecule. In practice this means that at least one of the groups R.sup.3
or R.sup.4 should be a hydrocarbyl group of at least 4 carbon atoms. In
one embodiment, R.sup.1 and R.sup.2 can be independently hydrocarbyl
groups (e.g., aliphatic hydrocarbyl groups such as alkyl groups) of 1 to
about 50 carbon atoms, and in one embodiment 1 to about 30 carbon atoms,
and in one embodiment 1 to about 18 carbon atoms, and in one embodiment 1
to about 12 carbon atoms, and in one embodiment 1 to about 8 carbon atoms.
In one embodiment the thiocarbamate is a compound represented by the formul
a
R.sup.1 R.sup.2 --N--C (S)--S--CH.sub.2 CH.sub.2 --C(O)--OR.sup.5(D-II)
wherein in Formula (D-II) R.sup.1, R.sup.2 and R.sup.5 are independently
hydrocarbyl (e.g., alkyl) groups. These hydrocarbyl groups can have from 1
to about 18 carbon atoms, and in one embodiment 1 to about 12 carbon
atoms, and in one embodiment 1 to about 8 carbon atoms, and in one
embodiment 1 to about 4 carbon atoms. These compounds include
S-carbomethoxyethyl-N,N-dibutyl dithiocarbamate which can be represented
by the formula
(C.sub.4 H.sub.9).sub.2 N--C(S)--S--CH.sub.2 CH.sub.2 C(O)--OCH.sub.3(D-III
)
Materials of this type can be prepared by a process described in U.S. Pat.
No. 4,758,362. Briefly, these materials are prepared by reacting an amine,
carbon disulfide or carbonyl sulfide, or source materials for these
reactants, and a reactant containing an activated,
ethylenically-unsaturated bond or derivatives thereof. These reactants are
charged to a reactor and stirred, generally without heating, since the
reaction is normally exothermic. Once the reaction reaches the temperature
of the exotherm (typically 40-65.degree. C.), the reaction mixture is held
at the temperature to insure complete reaction. After a reaction time of
typically 3-5 hours, the volatile materials are removed under reduced
pressure and the residue is filtered to yield the final product.
The relative amounts of the reactants used to prepare these compounds are
not critical. The charge ratios to the reactor can vary where economics
and the amount of the product desired are controlling factors. Thus, the
molar charge ratio of the amine to the CS.sub.2 or COS reactant to the
ethylenically unsaturated reactant may vary in the ranges 5:1:1 to 1:5:1
to 1:1:5. In one embodiment, the charge ratios of these reactants is
1:1:1.
In the case where a is 1, the activating group Z is separated from the
sulfur atom by a methylene group. Materials of this type can be prepared
by reaction of sodium dithiocarbamate with a chlorine-substituted
material. Such materials are described in greater detail in U.S. Pat. No.
2,897,152, which is incorporated herein by reference.
The following example illustrates the preparation of a thiocarbamate (D)
that can be used with this invention.
EXAMPLE D-1
Carbon disulfide (79.8 grams, 1.05 moles) and methyl acrylate (86 grams,
1.0 mole) are placed in a reactor and stirred at room temperature.
Di-n-butylamine (129 grams, 1.0 mole) is added dropwise to the mixture.
The resulting reaction is exothermic, and the di-n-butylamine addition is
done at a sufficient rate to maintain the temperature at 55.degree. C.
After the addition of di-n-butylamine is complete, the reaction mixture is
maintained at 55.degree. C. for four hours. The mixture is blown with
nitrogen at 85.degree. C. for one hour to remove unreacted starting
material. The reaction mixture is filtered through filter paper, and the
resulting product is a viscous orange liquid.
(E) Organic Sulfide.
The organic sulfides (E) that are useful with this invention are compounds
represented by the formula
T.sup.1 --C(X.sup.1)--S--(S).sub.n --C(X.sup.2)--T.sup.2 (E-I)
wherein in Formula (E-I), T.sup.1 and T.sup.2 are independently R, OR, SR
or NRR wherein each R is independently a hydrocarbyl group, X.sub.1 and
X.sup.2 are independently O or S, and n is zero to 3. In one embodiment,
X.sup.1 and X.sup.2 are each S. In one embodiment, n is 1 to 3, and in one
embodiment, n is 1. Thus, compounds represented by the formula
T.sup.1 --C(S)--S--S--C(S)--T.sup.2 (E-II)
wherein in Formula (E-II), T.sup.1 and T.sup.2 are as defined above can be
used. In one embodiment, each R is a hydrocarbyl group of 1 to about 50
carbon atoms, and in one embodiment 1 to about 40 carbon atoms, and in one
embodiment 1 to about 30 carbon atoms, and in one embodiment 1 to about 20
carbon atoms. In one embodiment, each R is independently methyl, ethyl,
propyl, isopropyl, n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, isooctyl,
decyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl,
alkylphenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl
or alkylnaphthylalkyl.
In one embodiment, the organic sulfide is a compound represented by the
formula:
R--C(O)--S--(S).sub.n --C(O)--R (E-III)
wherein in Formula (E-III), R and n are as defined above, with compounds
wherein n is 1 being especially useful.
In one embodiment, the organic sulfide is a compound represented by the
formula
RO--C(S)--S--(S).sub.n --C(S)--OR (E-IV)
wherein in Formula (E-IV), R and n are as defined above, with compounds
wherein n is 1 being useful.
In one embodiment, the organic sulfide is a compound represented by the
formula
RS--C(S)--S--(S).sub.n --C(S)--SR (E-V)
wherein in Formula (E-V), R and n are as defined above, with compounds
wherein n is 1 being especially useful.
In one embodiment, the organic sulfide is a compound represented by the
formula
RRN--C(S)--S--(S).sub.n --C(S)--NRR (E-VI)
wherein in Formula (E-VI), R and n are as defined above, with compounds
wherein n is 1 being especially useful.
These compounds are known and can be prepared by conventional techniques.
For example, an appropriate mercaptan, alcohol or amine can first be
reacted with an alkali metal reagent (e.g., NaOH, KOH) and carbon
disulfide to form the corresponding thiocarbonate or dithiocarbamate. The
thiocarbonate or dithiocarbamate is then reacted with an oxidizing agent
(e.g., hydrogen peroxide, cobalt maleonitriledithioate, K.sub.2
Fe(CN).sub.6, FeCl.sub.3, dimethylsulfoxide, dithiobis(thioformate),
copper sulfate, etc.) to form a disulfide, or with sulfur dichloride or
sulfur monochloride to form a trisulfide or tetrasulfide, respectively.
The oxygen-containing analogs of these compounds wherein X.sup.1 and
X.sup.2 in Formula (E-I) are oxygen can be prepared by treating the
sulfur-containing compounds with water or steam.
The mercaptans that can be used include the hydrocarbyl mercaptans
represented by the formula R-S-H, wherein R is as defined above in Formula
(E-I). In one embodiment, R is an alkyl, an alkenyl, cycloalkyl, or
cycloalkenyl group. R may be an aryl (e.g., phenyl, naphthyl), alkylaryl,
arylalkyl or alkylaryl alkyl group. R may also be a haloalkyl,
hydroxyalkyl, or hydroxyalkyl-substituted (e.g., hydroxymethyl,
hydroxyethyl, etc.) aliphatic group. In one embodiment, R contains from
about 2 to about 30 carbon atoms, or from about 2 to about 24, or from
about 3 to about 18 carbon atoms. Examples include butyl mercaptan, amyl
mercaptan, hexyl mercaptan, octyl mercaptan, 6-hydroxymethyloctanethiol,
nonyl mercaptan, decyl mercaptan, 10-amino-dodecanethiol, dodecyl
mercaptan, 10-hydroxymethyl-tetradecanethiol, and tetradecyl mercaptan.
Alcohols used to prepare the organic sulfides of Formula (E-I) can be any
of those described above under the subtitle "(A) Mixed Polysulfides."
The amines that can be used include those described above under the
subtitles "(A) Mixed Polysulfides" and "(B) Acylated Nitrogen-Containing
Compounds."
The following examples illustrate the preparation of organic sulfides (E)
that are useful with this invention.
EXAMPLE E-1
Di-n-butylamine (129 grams, 1 equivalent) is charged to a reactor. Carbon
disulfide (8.4 grams, 1.1 equivalents) is added dropwise over a period of
2.5 hours. The resulting reaction is exothermic but the temperature of the
reaction mixture is maintained below 50.degree. C. using an ice bath.
After the addition of carbon disulfide is complete the mixture is
maintained at room temperature for one hour with stirring. A 50% aqueous
sodium hydroxide solution (40 grams) is added and the resulting mixture is
stirred for one hour. A 30% aqueous hydrogen peroxide solution (200 grams)
is added dropwise. The resulting reaction is exothermic but the
temperature of the reaction mixture is maintained below 50.degree. C.
using an ice bath. The mixture is transferred to a separatory funnel.
Toluene (800 grams) is added to the mixture. The organic layer is
separated from the product and washed with one liter of distilled water.
The separated and washed organic layer is dried over sodium carbonate and
filtered through diatomaceous earth. The mixture is stripped on a rotary
evaporator at 77.degree. C. and 20 mm Hg to provide the desired
dithiocarbamate disulfide product which is in the form of a dark orange
liquid.
EXAMPLE E-2
Di-n-butyl amine (1350 grams) is charged to a reactor. Carbon disulfide
(875 grams) is added dropwise while maintaining the mixture below
50.degree. C. A 50% aqueous sodium hydroxide solution (838 grams) is added
dropwise. A 30% aqueous H.sub.2 O.sub.2 solution (2094 grams) is added
dropwise. The reaction mixture exotherms. An aqueous layer and an organic
layer form. The aqueous layer is separated from the organic layer. Diethyl
ether (1000 grams) is mixed with the aqueous layer to extract organic
material from it. The diethyl ether containing extract is added to the
organic layer. The resulting mixture is stripped at 70.degree. C. and 20
mm Hg, and then filtered through diatomaceous earth to provide the desired
disulfide product which is in the form of a brown liquid.
EXAMPLE E-3
A mixture of 1-octanethiol (200 grams), 50% aqueous NaOH solution (110
grams) and toluene (200 grams) is prepared and heated to reflux
(120.degree. C.) to remove water. The mixture is cooled to room
temperature and carbon disulfide (114.5 grams) is added. A 30% aqueous
H.sub.2 O.sub.2 solution (103 grams) is added dropwise while maintaining
the temperature below 50.degree. C. Diethyl ether is added and then
extracted. The organic layer is isolated, washed with distilled water,
dried and chromotographed using hexane to provide the desired disulfide
product which is in the form of a yellow liquid.
EXAMPLE E-4
(a) A mixture of 4000 grams of dodecyl mercaptan, 1600 grams of a 50%
aqueous NaOH solution and 2000 grams of toluene is prepared and heated to
125.degree. C. to remove 1100 grams of water. The reaction mixture is
cooled to 40.degree. C. and 1672 grams of carbon disulfide are added. The
mixture is heated to 70.degree. C. and maintained at that temperature for
8 hours. The mixture is filtered using diatomaceous earth and stripped at
100.degree. C. and 20 mm Hg to form the desired product which is in the
form of a red liquid.
(b) 200 grams of the product from part (a) and 200 grams of hexane are
placed in a reactor and cooled to 10.degree. C. 130 grams of a 30% aqueous
H.sub.2 O.sub.2 solution are added dropwise while maintaining the
temperature below 45.degree. C. The mixture is extracted with diethyl
ether. The organic portion is washed with water, dried with Na.sub.2
CO.sub.3, filtered, and heated under azeotropic conditions to remove water
and provide the desired disulfide product which is in the form of a bright
red liquid.
EXAMPLE E-5
1700 grams of methylpentanol and 407 grams of potassium hydroxide are
placed in a reactor. The mixture is heated under reflux conditions to
remove 130-135 grams of water. The mixture is cooled to 50.degree. C., and
627 grams of carbon disulfide are added. 750 grams of a 30% aqueous
H.sub.2 O.sub.2 solution are added dropwise. The mixture exotherms, and an
aqueous layer and an organic layer are formed. The aqueous layer is
separated from the organic layer. The organic layer is stripped at
100.degree. C. and 20 mm Hg and filtered to provide the desired disulfide
product which is in the form of an orange liquid.
EXAMPLE E-6
1100 grams of methylpentyl alcohol and 863 grams of a 50% aqueous NaOH
solution are placed in a reactor and heated to 120.degree. C. to remove
430 grams of water. The mixture is cooled to 50.degree. C. and 925 grams
of carbon disulfide are added. 623 grams of a 30% aqueous H.sub.2 O.sub.2
solution are added dropwise. The resulting reaction is exothermic, and an
aqueous and an organic layer are formed. The aqueous layer is separated.
The organic layer is stripped at 100.degree. C. and 20 mm Hg and filtered
to provide the desired disulfide product.
Lubricating Compositions and Functional Fluids.
The lubricating compositions and functional fluids of the present invention
are based on diverse oils of lubricating viscosity, including natural and
synthetic lubricating oils and mixtures thereof. The lubricating
compositions may be lubricating oils and greases useful in industrial
applications and in automotive engines, transmissions and axles. These
lubricating compositions are effective in a variety of applications
including crankcase lubricating oils for spark-ignited and
compression-ignited internal combustion engines, including automobile and
truck engines, two-cycle engines, aviation piston engines, marine and
low-load diesel engines, and the like. Also, automatic transmission
fluids, farm tractor fluids, transaxle lubricants, gear lubricants,
metalworking lubricants, hydraulic fluids, and other lubricating oil and
grease compositions can benefit from the incorporation of the compositions
of this invention. The inventive lubricating compositions are particularly
effective as engine lubricating oils having enhanced antiwear properties.
The lubricant compositions of this invention employ an oil of lubricating
viscosity which is generally present in a major amount (i.e. an amount
greater than about 50% by weight). Generally, the oil of lubricating
viscosity is present in an amount greater than about 60%, or greater than
about 70%, or greater than about 80% by weight of the composition.
The natural oils useful in making the inventive lubricants and functional
fluids include animal oils and vegetable oils (e.g., castor oil, lard oil)
as well as mineral lubricating oils such as liquid petroleum oils and
solvent treated or acid-treated mineral lubricating oils of the
paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of
lubricating viscosity derived from coal or shale are also useful.
Synthetic lubricating oils include hydrocarbon oils such as polymerized
and interpolymerized olefins (e.g., polybutylenes, polypropylenes,
propylene-isobutylene copolymers, etc.); poly(1-hexenes), poly-(1
-octenes), poly(1-decenes), etc. and mixtures thereof; alkylbenzenes
(e.g., dodecyl-benzenes, tetradecylbenzenes, dinonylbenzenes,
di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,
terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and
alkylated diphenyl sulfides and the derivatives, analogs and homologs
thereof and the like.
Alkylene oxide polymers and interpolymers and derivatives thereof where the
terminal hydroxyl groups have been modified by esterification,
etherification, etc., constitute another class of known synthetic
lubricating oils that can be used. These are exemplified by the oils
prepared through polymerization of ethylene oxide or propylene oxide, the
alkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,
methyl-polyisopropylene glycol ether having an average molecular weight of
about 1000, diphenyl ether of polyethylene glycol having a molecular
weight of about 500-1000, diethyl ether of polypropylene glycol having a
molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic
esters thereof, for example, the acetic acid esters, mixed C.sub.3-8 fatty
acid esters, or the C.sub.13 Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils that can be used
comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic
acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic
acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid
dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.)
with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl
alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol
monoether, propylene glycol, etc.) Specific examples of these esters
include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate,
dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl
phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester
of linoleic acid dimer, the complex ester formed by reacting one mole of
sebacic acid with two moles of tetraethylene glycol and two moles of
2-ethylhexanoic acid and the like.
Esters useful as synthetic oils also include those made from C.sub.5 to
C.sub.12 monocarboxylic acids and polyols and polyol ethers such as
neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol,
tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, polyaryl-,polyalkoxy-, or
polyaryloxy-siloxane oils and silicate oils comprise another useful class
of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl
silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methylhexyl)silicate,
tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2-pentoxy)disiloxane,
poly(methyl) siloxanes, poly-(methylphenyl)siloxanes, etc.). Other
synthetic lubricating oils include liquid esters of phosphorus-containing
acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of
decanephosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and refined oils, either natural or synthetic (as well
as mixtures of two or more of any of these) of the type disclosed
hereinabove can be used in the lubricants of the present invention.
Unrefined oils are those obtained directly from a natural or synthetic
source without further purification treatment. For example, a shale oil
obtained directly from retorting operations, a petroleum oil obtained
directly from primary distillation or ester oil obtained directly from an
esterification process and used without further treatment would be an
unrefined oil. Refined oils are similar to the unrefined oils except they
have been further treated in one or more purification steps to improve one
or more properties. Many such purification techniques are known to those
skilled in the art such as solvent extraction, secondary distillation,
acid or base extraction, filtration, percolation, etc. Rerefined oils are
obtained by processes similar to those used to obtain refined oils applied
to refined oils which have been already used in service. Such rerefined
oils are also known as reclaimed or reprocessed oils and often are
additionally processed by techniques directed to removal of spent
additives and oil breakdown products.
In one embodiment, component (A) is employed in the lubricant or functional
fluid at a concentration in the range of about 0.001% to about 5% by
weight, and in one embodiment about 0.01% to about 3%, and in one
embodiment about 0.02% to about 2% by weight based on the total weight of
the lubricant or functional fluid. In one embodiment, component (B) is
employed in the lubricant or functional fluid at a concentration in the
range of about 0.01% to about 20% by weight, and in one embodiment from
about 0.1% to about 10%, and in one embodiment from about 0.5% to about
10% by weight based on the total weight of the lubricant or functional
fluid. In one embodiment, component (C) is employed in the lubricant or
functional fluid at a concentration in the range of up to about 20% by
weight, and in one embodiment from about 0.01 % to about 10%, and in one
embodiment from about 0.05% to about 5% by weight based on the total
weight of the lubricant or functional fluid. In one embodiment, component
(D) is employed in the lubricant or functional fluid at a concentration in
the range of up to about 10% by weight, and in one embodiment about 0.01%
to about 5%, and in one embodiment about 0.1% to about 3% by weight based
on the total weight of the lubricant or functional fluid. In one
embodiment, component (E) is employed in the lubricant or functional fluid
at a concentration in the range of up to about 10% by weight, and in one
embodiment about 0.001% to about 5% by weight, and in one embodiment about
0.01% to about 3%, and in one embodiment about 0.02% to about 2% by weight
based on the total weight of the lubricant or functional fluid.
In one embodiment the inventive lubricating compositions are useful as
engine lubricating oils or crankcase oils. These compositions may be
characterized by a phosphorus content of up to about 0.12% by weight, and
in one embodiment up to about 0.11% by weight, and in one embodiment up to
about 0.10% by weight, and in one embodiment up to about 0.09% by weight,
and in one embodiment up to about 0.08% by weight, and in one embodiment
up to about 0.05% by weight. In one embodiment the phosphorus content is
in the range of about 0.01% to about 0.12% by weight, and in one
embodiment about 0.01 % to about 0.10% by weight, and in one embodiment
about 0.02% to about 0.09% by weight and in one embodiment about 0.05% to
about 0.09% by weight.
When used for crankcase applications such as for gasoline and diesel
engines, the oil of lubricating viscosity can be selected to provide an
SAE crankcase viscosity number of 5W, 10W, 20W or 30W grade lubricants.
The lubricating compositions may also have a so-called multigrade rating
such as SAE 10W-30, 10W-40, 10W-50, etc. Multigrade lubricants may include
a minor viscosity improving amount of a viscosity improver which is
formulated with the oil of lubricating viscosity to provide the above
lubricant grades. Useful viscosity improvers include polyolefins, such as
polybutylene; rubbers, such as styrene-butadiene or styrene-isoprene; or
polyacrylates, such as polymethacrylates. Useful viscosity improvers that
are available commercially include Acryloid viscosity improvers available
from Rohm & Haas; Shellvis rubbers available from Shell Chemical; and
Lubrizol 3174 available from The Lubrizol Corporation.
In one embodiment, the inventive lubricating compositions and functional
fluids are used as gear oils. When used as such gear oils the use of
phosphorus-containing extreme pressure and/or antiwear agents other than
component (A) of this invention is reduced or eliminated. These gear oil
compositions generally contain less than about 0.5%, or less than about
0.25%, or less than about 0.1% by weight phosphorus, and in one
embodiment, less than about 0.05% by weight phosphorus.
In one embodiment, the oil of lubricating viscosity is selected to provide
a lubricating composition having a kinematic viscosity of at least about
3.5, or at least about 4.0 cSt at 100.degree. C. In one embodiment, the
oil of lubricating viscosity is selected to provide a lubricating
composition of at least an SAE gear oil viscosity number of about 60 or
about 65, more preferably about SAE 75. The lubricating composition may
also have a so-called multigrade rating such as SAE 60W-80, 65W-80, 65
W-90, 75W-80, 75W-90, 80W-90, 80W-140 or 85W-140.
The invention also provides for the use of lubricants and functional fluids
containing other additives in addition to components (A), (B), (C), (D)
and (E). Such additives include, for example, detergents and dispersants,
corrosion-inhibiting agents, antioxidants, viscosity improving agents,
extreme pressure (E.P.) agents, pour point depressants, friction
modifiers, fluidity modifiers, anti-foam agents, etc.
The inventive lubricating compositions and functional fluids can contain
one or more detergents or dispersants of the ash-producing or ashless
type. The ash-producing detergents are exemplified by oil-soluble neutral
and basic salts of alkali or alkaline earth metals with sulfonic acids,
carboxylic acids, or organic phosphorus acids characterized by at least
one direct carbon-to-phosphorus linkage such as those prepared by the
treatment of an olefin polymer (e.g., polyisobutene having a molecular
weight of 1000) with a phosphorizing agent such as phosphorus trichloride,
phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride
and sulfur, white phosphorus and a sulfur halide, or phosphorothioic
chloride. The most commonly used salts of such acids are those of sodium,
potassium, lithium, calcium, magnesium, strontium and barium.
Ashless detergents and dispersants are so called despite the fact that,
depending on its constitution, the dispersant may upon combustion yield a
non-volatile material such as boric oxide or phosphorus pentoxide;
however, it does not ordinarily contain metal and therefore does not yield
a metal-containing ash on combustion. Many types are known in the art, and
any of them are suitable for use in the lubricant compositions and
functional fluids of this invention. The following are illustrative:
(1) Reaction products of carboxylic acids (or derivatives thereof)
containing at least about 34 and preferably at least about 54 carbon atoms
with nitrogen containing compounds such as amine, organic hydroxy
compounds such as phenols and alcohols, and/or basic inorganic materials.
Examples of these "carboxylic dispersants" are described in many U.S. Pat.
Nos. including 3,219,666; 4,234,435; and 4,938,881.
(2) Reaction products of relatively high molecular weight aliphatic or
alicyclic halides with amines, preferably oxyalkylene polyamines. These
may be characterized as "amine dispersants" and examples thereof are
described for example, in the following U.S. Pat. Nos. 3,275,554;
3,438,757; 3,454,555; and 3,565,804.
(3) Reaction products of alkyl phenols in which the alkyl group contains at
least about 30 carbon atoms with aldehydes (especially formaldehyde) and
amines (especially polyalkylene polyamines), which may be characterized as
"Mannich dispersants." The materials described in the following U.S. Pat.
Nos. are illustrative: 3,649,229; 3,697,574; 3,725,277; 3,725,480;
3,726,882; and 3,980,569.
(4) Products obtained by post-treating the amine or Mannich dispersants
with such reagents as urea, thiourea, carbon disulfide, aldehydes,
ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides,
nitriles, epoxides, boron compounds, phosphorus compounds or the like.
Exemplary materials of this kind are described in the following U.S. Pat.
Nos. 3,639,242; 3,649,229; 3,649,659; 3,658,836; 3,697,574; 3,702,757;
3,703,536; 3,704,308; and 3,708,422.
(5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate,
vinyl decyl ether and high molecular weight olefinswith monomers
containing polar substituents, e.g., aminoalkyl acrylates or acrylamides
and poly-(oxyethylene)-substituted acrylates. These may be characterized
as "polymeric dispersants" and examples thereof are disclosed in the
following U.S. Pat. Nos. 3,329,658; 3,449,250; 3,519,565; 3,666,730;
3,687,849; and 3,702,300.
The above-noted patents are incorporated by reference herein for their
disclosures of ashless dispersants.
The inventive lubricating compositions and functional fluids can contain
one or more extreme pressure, corrosion inhibitors and/or oxidation
inhibitors in addition to those that would be considered as being within
the scope of the above-discussed components. Extreme pressure agents and
corrosion- and oxidation-inhibiting agents which may be included in the
lubricants and functional fluids of the invention are exemplified by
chlorinated aliphatic hydrocarbons such as chlorinated wax; organic
sulfides and polysulfides such as benzyl disulfide,
bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester
of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and
sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction
product of a phosphorus sulfide with turpentine or methyl oleate; metal
thiocarbamates, such as zinc dioctyidithiocarbamate, and barium
heptylphenyidithiocarbamate; dithiocarbamate esters from the reaction
product of dithiocarbamic acid and acrylic, methacrylic, maleic, fumaric
or itaconic esters; dithiocarbamate containing amides prepared from
dithiocarbamic acid and an acrylamide; alkylene-coupled dithiocarbamates;
sulfur-coupled dithiocarbamates. Many of the above-mentioned extreme
pressure agents and oxidation-inhibitors also serve as antiwear agents.
Pour point depressants are a useful type of additive often included in the
lubricating oils and functional fluids described herein. The use of such
pour point depressants in oil-based compositions to improve low
temperature properties of oil-based compositions is well known in the art.
See, for example, page 8 of "Lubricant Additives" by C. V. Smallheer and
R. Kennedy Smith (Lezius Hiles Co. publishers, Cleveland, Ohio, 1967).
Examples of useful pour point depressants are polymethacrylates;
polyacrylates; polyacrylamides; condensation products of haloparaffin
waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers
of dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers. A
specific pour point depressant that can be used is the product made by
alkylating naphthalene with polychlorinated paraffin and C.sub.16
-C.sub.18 alpha-olefin. Pour point depressants useful for the purposes of
this invention, techniques for their preparation and their uses are
described in U.S. Pat. Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022;
2,191,498; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 which are herein
incorporated by reference for their relevant disclosures.
Anti-foam agents are used to reduce or prevent the formation of stable
foam. Typical anti-foam agents include silicones or organic polymers.
Additional antifoam compositions are described in "Foam Control Agents,"
by Henry T. Kemer (Noyes Data Corporation, 1976), pages 125-162.
Each of the foregoing additives, when used, is used at a functionally
effective amount to impart the desired properties to the lubricant or
functional fluid. Thus, for example, if an additive is a dispersant, a
functionally effective amount of this dispersant would be an amount
sufficient to impart the desired dispersancy characteristics to the
lubricant or functional fluid. Similarly, if the additive is an
extreme-pressure agent, a functionally effective amount of the
extreme-pressure agent would be a sufficient amount to improve the
extreme-pressure characteristics of the lubricant or functional fluid.
Generally, the concentration of each of these additives, when used, ranges
from about 0.001% to about 20% by weight, and in one embodiment about
0.01% to about 10% by weight based on the total weight of the lubricant or
functional fluid.
The lubricant compositions of the present invention may be in the form of
lubricating oils or greases in which any of the above-described oils of
lubricating viscosity can be employed as a vehicle. Where the lubricant is
to be used in the form of a grease, the lubricating oil generally is
employed in an amount sufficient to balance the total grease composition
and generally, the grease compositions will contain various quantities of
thickening agents and other additive components of the type described
above to provide desirable properties. Generally, the greases will contain
from about 0.01 to about 20-30% of such additive components.
A wide variety of thickening agents can be used in the preparation of the
greases of this invention. Included among the thickening agents are alkali
and alkaline earth metal soaps of fatty acids and fatty materials having
from about 12 to about 30 carbon atoms. The metals are typified by sodium,
lithium, calcium and barium. Examples of fatty materials include stearic
acid, hydroxy stearic acid, stearin, oleic acid, palmetic acid, myristic
acid, cottonseed oil acids, and hydrogenated fish oils.
Other thickening agents include salt and salt-soap complexes as calcium
stearate-acetate (U.S. Pat. No. 2,197,263), barium stearate acetate (U.S.
Pat. No. 2,564,561), calcium stearate-caprylate-acetate complexes (U.S.
Pat. No. 2,999,065), calcium caprylate-acetate (U.S. Pat. No. 2,999,066),
and calcium salts and soaps of low-,intermediate- and high-molecular
weight acids and of nut oil acids.
Useful thickening agents employed in the grease compositions are
essentially hydrophilic in character, but which have been converted into a
hydrophobic condition by the introduction of long chain hydrocarbon
radicals onto the surface of the clay particles prior to their use as a
component of a grease composition, as, for example, by being subjected to
a preliminary treatment with an organic cationic surface-active agent,
such as an onium compound. Typical onium compounds are tetraalkylammonium
chlorides, such as dimethyl dioctadecyl ammonium chloride, dimethyl
dibenzyl ammonium chloride and mixtures thereof This method of conversion,
being well known to those skilled in the art, and is believed to require
no further discussion. More specifically, the clays which are useful as
starting materials in forming the thickening agents to be employed in the
grease compositions, can comprise the naturally occurring chemically
unmodified clays. These clays are crystalline complex silicates, the exact
composition of which is not subject to precise description, since they
vary widely from one natural source to another. These clays can be
described as complex inorganic silicates such as aluminum silicates,
magnesium silicates, barium silicates, and the like, containing, in
addition to the silicate lattice, varying amounts of cation-exchangeable
groups such as sodium. Hydrophilic clays which are particularly useful for
conversion to desired thickening agents include montmorillonite clays,
such as bentonite, attapulgite, hectorite, illite, saponite, sepiolite,
biotite, vermiculite, zeolite clays, and the like. The thickening agent is
generally employed in an amount from about 0.5 to about 30% by weight, and
in one embodiment from about 3% to about 15% by weight of the total grease
composition.
Component (A), and optional components (B) to (E) of the inventive
compositions as well as one of the other above-discussed additives or
other additives known in the art can be added directly to the lubricant or
functional fluid. In one embodiment, however, they are diluted with a
substantially inert, normally liquid organic diluent such as mineral oil,
naphtha, benzene, toluene or xylene to form an additive concentrate which
is then added to the base oil to form the lubricant or functional fluid.
These concentrates usually contain from about 1% to about 99% by weight,
and in one embodiment about 10% to about 90% by weight of component (A)
and, optionally, one or more of components (B) to (E) as well as one or
more other additives known in the art or described hereinabove. The
remainder of the concentrate is the substantially inert normally liquid
diluent.
The following Examples 1-20 illustrate lubricating compositions and
functional fluids within the scope of the invention.
______________________________________
wt. %
______________________________________
Example 1
Product of Example A-1
0.5
Base oil Remainder
Example 2
Product of Example A-2
1.0
Base oil Remainder
Example 3
Product of Example A-3
1.4
Base oil Remainder
Example 4
Product of Example A-4
0.7
Base oil Remainder
Example 5
Product of Example A-5
2.0
Base oil Remainder
Example 6
Product of Example A-1
0.5
Product of Example B-1
4.0
Base oil Remainder
Example 7
Product of Example A-2
1.5
Product of Example B-2
5.0
Base oil Remainder
Example 8
Product of Example A-3
1.0
Product of Example B-1
5.0
Base oil Remainder
Example 9
Product of Example A-4
0.3
Product of Exampie B-2
4.5
Base oil Remainder
Example 10
Product of Example A-5
1.0
Product of Example B-1
5.5
Base oil Remainder
Example 11
Product of Example A-1
1.1
Product of Example B-2
6.5
Base oil Remainder
Example 12
Product of Example A-1
0.9
Product of Example C-1
0.7
Base oil Remainder
Example 13
Product of Example A-1
0.8
Product of Example C-3
1.4
Base oil Remainder
Example 14
Product of Example A-1
1.2
Product of Example C-7
0.5
Base oil Remainder
Example 15
Product of Example A-1
1.2
Product of Example D-1
0.6
Base oil Remainder
Example 16
Product of Example A-1
0.6
Product of Example E-1
0.5
Base oil Remainder
Example 17
Product of Example A-1
1.5
Product of Example B-1
4.5
Product of Example C-1
0.5
Base oil Remainder
Example 18
Product of Example A-1
0.5
Product of Example B-1
5.5
Product of Example C-1
1.0
Product of Example D-1
0.5
Base oil Remainder
Example 19
Product of Example A-1
1.0
Product of Example B-1
5.5
Product of Example C-1
0.5
Product of Example D-1
0.25
Product of Example E-1
0.25
Base oil Remainder
Example 20
Product of Example A-1
0.5
Product of Example B-1
5.0
Product of Example B-2
1.5
Product of Example C-1
0.5
Product of Example D-1
0.5
Base oil Remainder
______________________________________
Examples 21-30 disclosed in Table I are provided for the purpose of further
illustrating lubricating compositions and functional fluids within the
scope of the invention. These compositions are useful as engine
lubricating oil compositions. In Table I all numerical values, except for
the concentration of the silicone antifoam agent, are in percent by
weight. The concentration of the silicone antifoam agent is in parts per
million, ppm.
TABLE I
__________________________________________________________________________
Example No. 21 22 23 24 25 26 27 28 29 30
__________________________________________________________________________
Base oil (85% 100 N + 15% 150 N)
82.0
82.25
82.0
82.25
82.0
82.25
82.0
82.25
82.0
82.25
Product of Example A-1
0.5
0.25
-- -- -- -- -- -- -- --
Product of Example A-2
-- -- 0.5
0.25
-- -- -- -- -- --
Product of Example A-3
-- -- -- -- 0.5
0.25
-- -- -- --
Product of Example A-4
-- -- -- -- -- -- 0.5
0.25
-- --
Product of Example A-5
-- -- -- -- -- -- -- -- 0.5
0.25
Product of Example B-1
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
Product of Example B-2
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
Product of Example C-1
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
Overbased Mg sulfonate,
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
metallsulfonate ratio = 14.7,
oil content = 42%
Overbased Ca sulfonate,
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
metal/sulfonate ratio = 1.2,
oil content = 50%
Overbased Na succinate,
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
oil content = 49%
Ca overbased sulfur
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
coupled alkyl phenol,
oil content = 39%
Olefin copolymer VI improver
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
Alkylated diphenylamine
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
Polymethacrylate pour point
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
depressant
Sulfur monochloride reacted
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
with alpha olefin mixture
followed by contact with
sodium disulfide
Vegetable oil 0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
Diluent oil 8.4
8.4
8.4
8.4
8.4
8.4
8.4
8.4
8.4
8.4
Silicone antifoam agent, ppm
18 18 18 18 18 18 18 18 18 18
__________________________________________________________________________
While the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications thereof
will become apparent to those skilled in the art upon reading the
specification. Therefore, it is to be understood that the invention
disclosed herein is intended to cover such modifications as fall within
the scope of the appended claims.
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